Polyphenylene ether resin composition and molded article

Abstract

A polyphenylene ether-based resin composition according to one embodiment of the present invention comprises 100 parts by mass of a polyphenylene ether-containing resin (A) containing at least more than 80% by mass of a polyphenylene ether-based resin (a), and 100 parts by mass of a polyphenylene ether-containing resin (B) containing at least more than 80% by mass of a polyphenylene ether-based resin (a). The flame retardant composition contains 5-25 parts by mass of an inorganic filler (c), 15-27 parts by mass of a phosphorus-based flame retardant (d), 0.3-7 parts by mass of a polyolefin resin (e) having an ethylene-derived skeleton, 3-20 parts by mass of a tracking resistance improver (f), and 0.5-3 parts by mass of a phosphorus-based stabilizer (g). The mass ratio of the polyolefin resin (e) to the phosphorus component in the polyphenylene ether resin composition is 0.2-2.65. The polyolefin resin (e) has a melt flow rate, as measured in accordance with JIS K7210, of 0.5-100 g / 10 minutes under measurement conditions of a temperature of 190 DEG C and a load of 2.16 kg.

Description

Technical Field

[0001] The present invention relates to a polyphenylene ether resin composition and a molded product. Background Art

[0002] Polyphenylene ether resin is a resin having excellent properties such as heat resistance, flame retardancy, electrical properties, dimensional stability, etc., and also has excellent properties such as low specific gravity and hydrolysis resistance. In addition, polyphenylene ether resin can be improved in molding processability and impact resistance by blending various resins such as styrene resin.

[0003] Polyphenylene ether resin compositions containing such polyphenylene ether resins and the like have been widely used as materials for various purposes such as electrical components, electronic equipment components, and vehicle components. Various properties are required for polyphenylene ether resin compositions depending on their use. For example, when a polyphenylene ether resin composition is used as a material for a protective housing for protecting a battery cell having a battery pack or the like, the polyphenylene ether resin composition is required to have high tracking resistance in addition to flame retardancy and impact resistance, which are required as a protective housing for a battery cell.

[0004] For example, as a polyphenylene ether-based resin composition having high tracking resistance, Patent Document 1 discloses a resin composition comprising a polyphenylene ether-based resin and at least one selected from a hydrogenated block copolymer having a specific structure and a modified product of the hydrogenated block copolymer.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2019-137742 Summary of the invention

[0008] Problem that the invention aims to solve

[0009] Generally, the tracking resistance of a polyphenylene ether resin composition can be improved by mixing a polyolefin resin having excellent electrical properties. However, as described above, polyolefin resins are effective in improving the tracking resistance, but are easily flammable, and therefore, excessive mixing may impair the flame retardancy of the polyphenylene ether resin composition.

[0010] In addition, the flame retardancy of the polyphenylene ether resin composition can be improved by adding a phosphorus-based flame retardant such as a condensed phosphate ester. However, excessive addition of a phosphorus-based flame retardant may reduce the impact resistance of the polyphenylene ether resin composition.

[0011] Furthermore, depending on the use of the polyphenylene ether resin composition, high mechanical strength is sometimes required. For example, the mechanical strength of the polyphenylene ether resin composition can be enhanced by adding inorganic fillers such as glass fibers. However, the addition of inorganic fillers may significantly reduce the tracking resistance of the polyphenylene ether resin composition.

[0012] As described above, the conventional polyphenylene ether-based resin composition exemplified in Patent Document 1 has difficulty in achieving both high tracking resistance and excellent flame retardancy and impact resistance required for applications such as protective cases of battery cells.

[0013] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyphenylene ether-based resin composition and a molded article that can achieve both high tracking resistance and excellent flame retardancy and impact resistance.

[0014] Solutions for solving problems

[0015] As a result of repeated and in-depth studies by the present inventors to solve the above-mentioned problems, a polyolefin resin having a skeleton derived from ethylene was discovered as a component capable of improving the balance between impact resistance and tracking resistance of a polyphenylene ether resin composition. By blending the above-mentioned polyolefin resin, an inorganic filler, a phosphorus-based flame retardant, a tracking resistance improver and a phosphorus-based stabilizer in a specific ratio with a resin component containing at least a polyphenylene ether resin, a polyphenylene ether resin composition having high tracking resistance as well as excellent flame retardancy and impact resistance was obtained, thereby completing the present invention.

[0016] That is, in order to solve the above-mentioned problems and achieve the purpose, the polyphenylene ether resin composition of the present invention is characterized in that it contains at least a polyphenylene ether resin (a), and contains 5 to 25 parts by mass of an inorganic filler (c), 15 to 27 parts by mass of a phosphorus flame retardant (d), 0.3 to 7 parts by mass of a polyolefin resin (e) having a skeleton derived from ethylene, 3 to 20 parts by mass of a tracking resistance improver (f), and 0.5 to 3 parts by mass of a phosphorus stabilizer (g), relative to 100 parts by mass of a polyphenylene ether-containing resin (A) containing more than 80% by mass of the polyphenylene ether resin (a), wherein the mass ratio of the polyolefin resin (e) to the phosphorus component in the polyphenylene ether resin composition is 0.2 to 2.65, and the melt flow rate of the polyolefin resin (e) measured in accordance with JIS K7210 is 0.5 to 100 g / 10 minutes under the measurement conditions of a temperature of 190° C. and a load of 2.16 kg.

[0017] The polyphenylene ether resin composition of the present invention is characterized in that, in the above invention, the polyphenylene ether-containing resin (A) contains 85 to 100% by mass of the polyphenylene ether resin (a) and 0 to 15% by mass of the styrene resin (b).

[0018] The polyphenylene ether resin composition of the present invention is characterized in that, in the above invention, the tracking resistance improver (f) comprises at least one selected from alkaline earth metal salts, metal hydroxides, nitrogen-containing compounds, inorganic acid metal compounds and layered double hydroxides.

[0019] Furthermore, the polyphenylene ether-based resin composition according to the present invention is characterized in that, in the above invention, the tracking resistance improver (f) is calcium carbonate.

[0020] Furthermore, the polyphenylene ether-based resin composition according to the present invention is characterized in that, in the above invention, the inorganic filler (c) includes at least one selected from the group consisting of glass fiber, mica, and talc.

[0021] Furthermore, the molded article according to the present invention is characterized in that it is formed from the polyphenylene ether-based resin composition according to any one of the above-mentioned inventions.

[0022] Furthermore, the molded article according to the present invention is characterized in that, in the above invention, it is a battery cell case.

[0023] Effects of the Invention

[0024] According to the present invention, there is provided an effect of providing a polyphenylene ether-based resin composition and a molded article capable of achieving both high tracking resistance and excellent flame retardancy and impact resistance. DETAILED DESCRIPTION

[0025] Hereinafter, suitable embodiments of the polyphenylene ether resin composition and molded article of the present invention are described in detail. It should be noted that the present invention is not limited to the embodiments shown below. In addition, in this specification, the expression "to" is used to include the numerical values ​​recorded before and after it as the lower limit and upper limit unless otherwise specified.

[0026] [Polyphenylene ether resin composition]

[0027] The polyphenylene ether-based resin composition according to the embodiment of the present invention (hereinafter referred to as PPE-based resin composition (Z)) is a resin composition containing at least a polyphenylene ether-based resin (a).

[0028] Specifically, the PPE resin composition (Z) contains, relative to 100 parts by mass of a polyphenylene ether-containing resin (A) containing more than 80% by mass of a polyphenylene ether-based resin (a), 5 to 25 parts by mass of an inorganic filler (c), 15 to 27 parts by mass of a phosphorus-based flame retardant (d), 0.3 to 7 parts by mass of a polyolefin resin (e), 3 to 20 parts by mass of a tracking resistance improver (f), and 0.5 to 3 parts by mass of a phosphorus-based stabilizer (g). In the PPE resin composition (Z), the polyolefin resin (e) is a polyolefin resin having a skeleton derived from ethylene, such as a polyethylene resin or an ethylene-propylene copolymer. In addition, the mass ratio of the polyolefin resin (e) in the PPE resin composition (Z) to the phosphorus component is 0.2 to 2.65.

[0029] Hereinafter, each component constituting the PPE-based resin composition (Z), the mass ratio of the polyolefin resin (e) to the phosphorus component in the PPE-based resin composition (Z), a molded article formed from the PPE-based resin composition (Z), etc. will be described in detail.

[0030] [Polyphenylene ether-containing resin]

[0031] First, a component of the PPE-based resin composition (Z) described in an embodiment of the present invention, namely, a polyphenylene ether-containing resin (A), is described in detail. The polyphenylene ether-containing resin (A) is a resin containing at least more than 80% by mass of a polyphenylene ether-based resin (a). For example, as the polyphenylene ether-containing resin (A), there can be listed a resin containing only a polyphenylene ether-based resin (a), a resin containing a polyphenylene ether-based resin (a) and a styrene-based resin (b) (i.e., a modified polyphenylene ether-based resin), a resin containing a resin component other than a styrene-based resin (b) and a polyphenylene ether-based resin (a), and the like.

[0032] Specifically, the polyphenylene ether-containing resin (A) contains a polyphenylene ether-based resin (a) as a main component. The main component mentioned here refers to the component with the largest content in the target component. In the present invention, the content ratio of the polyphenylene ether-based resin (a) exceeds 80% by mass as described above in 100% by mass of the polyphenylene ether-containing resin (A).

[0033] For example, a modified polyphenylene ether resin (hereinafter referred to as modified PPE resin) contains a polyphenylene ether resin (a) as a main component and further contains a styrene resin (b). The modified PPE resin may contain other resin components in addition to the polyphenylene ether resin (a) and the styrene resin (b) as required. In addition, the polyphenylene ether-containing resin (A) contains a polyphenylene ether resin (a) as a main component and further contains resin components in addition to the polyphenylene ether resin (a) and the styrene resin (b).

[0034] The PPE-based resin composition (Z) preferably contains 60 to 75% by mass of such a polyphenylene ether-containing resin (A). That is, the content of the polyphenylene ether-containing resin (A) in 100% by mass of the PPE-based resin composition (Z) is preferably 60 to 75% by mass, and more preferably 62 to 73% by mass. In addition, the polyphenylene ether-containing resin (A) preferably contains 81 to 100% by mass of a polyphenylene ether-based resin (a) and 0 to 19% by mass of a styrene-based resin (b), more preferably 83 to 100% by mass of a polyphenylene ether-based resin (a) and 0 to 17% by mass of a styrene-based resin (b), and further preferably 85 to 100% by mass of a polyphenylene ether-based resin (a) and 0 to 15% by mass of a styrene-based resin (b). By setting the content ratio of each of the polyphenylene ether-based resin (a) and the styrene-based resin (b) within the above range in 100% by mass of the polyphenylene ether-containing resin (A), the heat resistance, flame retardancy and mechanical strength of the PPE-based resin composition (Z) tend to be further improved.

[0035] [Polyphenylene ether resin (a)]

[0036] Next, the polyphenylene ether resin (a) described in the embodiment of the present invention is described in detail. The polyphenylene ether resin (a) is a resin component used in the PPE resin composition (Z) described in the embodiment of the present invention, and is contained in the PPE resin composition (Z) as the main component of the polyphenylene ether-containing resin (A). For example, the polyphenylene ether resin (a) is a polymer having a structural unit represented by the following general formula (1) in the main chain. The polyphenylene ether resin (a) may be a homopolymer or a copolymer.

[0037]

[0038] In the general formula (1), the two R a Each independently represents a hydrogen atom, a halogen atom, a primary alkyl group, a secondary alkyl group, an aryl group, an aminoalkyl group, a halogenated alkyl group, a hydrocarbyloxy group or a halogenated hydrocarbyloxy group. a cannot be hydrogen atoms at the same time. b Each independently represents a hydrogen atom, a halogen atom, a primary alkyl group, a secondary alkyl group, an aryl group, a halogenated alkyl group, a hydrocarbyloxy group or a halogenated hydrocarbyloxy group.

[0039] As R a and R b , preferably a hydrogen atom, a primary alkyl group, a secondary alkyl group or an aryl group. Suitable examples of primary alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, isopentyl, 2-methylbutyl, 2,3-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl or heptyl. Suitable examples of secondary alkyl groups include isopropyl, sec-butyl or 1-ethylpropyl. Among these, R aParticularly preferred are primary alkyl groups having 1 to 4 carbon atoms, secondary alkyl groups having 1 to 4 carbon atoms, or phenyl groups. b A hydrogen atom is particularly preferred.

[0040] Suitable homopolymers of the polyphenylene ether-based resin (a) include, for example, polymers of 2,6-dialkylphenylene ether, etc. Examples of the polymers of 2,6-dialkylphenylene ether include, for example, poly(2,6-dimethyl-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), poly(2,6-dipropyl-1,4-phenylene ether), poly(2-ethyl-6-methyl-1,4-phenylene ether), poly(2-methyl-6-propyl-1,4-phenylene ether), etc.

[0041] Examples of suitable copolymers of the polyphenylene ether-based resin (a) include 2,6-dialkylphenol / 2,3,6-trialkylphenol copolymers, graft copolymers obtained by graft-polymerizing poly(2,6-dimethyl-1,4-phenylene ether) with styrene, and graft copolymers obtained by graft-polymerizing styrene with 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymers. Examples of the 2,6-dialkylphenol / 2,3,6-trialkylphenol copolymers include 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymers, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymers, 2,6-diethylphenol / 2,3,6-trimethylphenol copolymers, and 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymers.

[0042] Among these, poly(2,6-dimethyl-1,4-phenylene ether) and 2,6-dimethylphenol / 2,3,6-trimethylphenol random copolymers are particularly preferred as the polyphenylene ether resin (a). In addition, as the polyphenylene ether resin (a), for example, as described in Japanese Patent Application Laid-Open No. 2005-344065, polyphenylene ether resins with specified terminal group numbers and copper content can also be suitably used.

[0043] Regarding the molecular weight of the polyphenylene ether resin (a), the above-mentioned intrinsic viscosity is preferably calculated as a viscosity-average molecular weight converted from the intrinsic viscosity measured at a temperature of 30°C using chloroform as a solvent, and is preferably 0.2 dl / g or more, and more preferably 0.3 dl / g or more. By setting the viscosity-average molecular weight of the polyphenylene ether resin (a) to the viscosity-average molecular weight when the above-mentioned intrinsic viscosity is 0.2 dl / g or more, there is a tendency for the mechanical strength of the PPE resin composition (Z) to be improved. In addition, the above-mentioned intrinsic viscosity is preferably 0.8 dl / g or less, and more preferably 0.6 dl / g or less. By setting the viscosity-average molecular weight of the polyphenylene ether resin (a) to the viscosity-average molecular weight when the above-mentioned intrinsic viscosity is 0.8 dl / g or less, the fluidity of the PPE resin composition (Z) is improved, and as a result, there is a tendency to facilitate the molding processing of the PPE resin composition (Z). Furthermore, by using two or more polyphenylene ether resins having different intrinsic viscosities in combination, the viscosity average molecular weight of the polyphenylene ether resin (a) can be adjusted to the viscosity average molecular weight when the intrinsic viscosity is within the range of 0.2 to 0.8 dl / g.

[0044] In addition, the method for producing the polyphenylene ether resin (a) is not particularly limited, and a known method can be used. For example, the polyphenylene ether resin (a) can be produced by oxidative polymerization of monomers such as 2,6-dimethylphenol in the presence of an amine copper catalyst. At this time, by selecting reaction conditions, the intrinsic viscosity can be controlled to a desired range. For example, the control of the intrinsic viscosity can be achieved by selecting conditions such as polymerization temperature, polymerization time, and catalyst amount.

[0045] In addition, as the polyphenylene ether-based resin (a), one kind of polyphenylene ether-based resin may be used alone, or two or more kinds of polyphenylene ether-based resins may be used in combination.

[0046] By making the PPE resin composition (Z) contain the above-mentioned polyphenylene ether resin (a), the heat resistance of the PPE resin composition (Z) can be improved. In an embodiment of the present invention, the heat resistance of the PPE resin composition (Z) is expressed by, for example, the load deflection temperature measured in accordance with JIS K7191-2 or ISO-75-2. The load deflection temperature of the PPE resin composition (Z) can be increased to a prescribed value or more by containing the above-mentioned polyphenylene ether resin (a). For example, the load deflection temperature of the PPE resin composition (Z) is preferably 100°C or more under the measurement condition of applying a load of 1.80MPa.

[0047] [Styrene resin (b)]

[0048] Next, the styrene resin (b) described in the embodiment of the present invention is described in detail. The styrene resin (b) is a resin component used in the PPE resin composition (Z) described in the embodiment of the present invention, and is contained in the PPE resin composition (Z) as a component of the polyphenylene ether-containing resin (A). In this case, the polyphenylene ether-containing resin (A) is a modified PPE resin. For example, as the styrene resin (b), polymers of styrene monomers, copolymers of styrene monomers and other copolymerizable monomers, and styrene graft copolymers can be listed.

[0049] More specifically, as the styrene resin (b), there can be listed resins such as polystyrene (PS), high-impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS resin), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), styrene-IPN type rubber copolymer, or mixtures thereof. In addition, the styrene resin (b) may have stereoregularity such as syndiotactic polystyrene. Among these, as the styrene resin (b), polystyrene and high-impact polystyrene are preferred, and high-impact polystyrene is particularly preferred from the viewpoint of improving the impact resistance of the PPE resin composition (Z).

[0050] In the embodiment of the present invention, the impact-resistant polystyrene used as the styrene resin (b) is obtained by, for example, polymerizing at least a styrene monomer in the presence of a rubber. Regarding the impact-resistant polystyrene, fine rubber-like particles are blended or graft-polymerized in a matrix of a styrene polymer. As the above-mentioned rubber, polybutadiene, styrene-butadiene copolymer, polyisoprene, ethylene-propylene copolymer, etc. can be listed. As the above-mentioned styrene polymer, polystyrene and copolymers of styrene and other copolymerizable monomers can be listed. Among them, polystyrene is preferred.

[0051] Examples of the styrene polymer include polymers composed of a repeating unit represented by the following general formula (2) and copolymers containing 50% by mass or more of a repeating unit represented by the following general formula (2) and other copolymerizable monomers.

[0052]

[0053] In the general formula (2), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Z represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom. n represents an integer of 1 to 5.

[0054] Examples of monomers other than styrene monomers that are copolymerizable with the styrene monomers include vinyl monomers such as acrylonitrile and methyl methacrylate.

[0055] The content of the rubber polymer component in the impact-resistant polystyrene is preferably 1% by mass or more, more preferably 4% by mass or more, and further preferably 8% by mass or more. In addition, the content of the rubber polymer component is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less. In addition, when the impact-resistant polystyrene contains monomer components other than styrene-based monomers, the sum of the contents of the rubber polymer component and the styrene-based monomer component in the impact-resistant polystyrene is preferably 85% by mass or more, and more preferably 90% by mass or more.

[0056] The rubber polymer component in the impact-resistant polystyrene is distributed in the entire polystyrene matrix in the form of particles, and is mainly formed by a plurality of cell structures. The volume average particle size of the particle-shaped rubber polymer component (hereinafter referred to as rubber particles) is preferably 0.1 to 2.0 μm, more preferably 0.2 to 1.5 μm, and further preferably 0.3 to 1.0 μm. By compounding the impact-resistant polystyrene containing rubber particles of such a volume average particle size, there is a tendency that the impact resistance, surface glossiness and colorability of the PPE-based resin composition (Z) are improved.

[0057] The volume average particle size of the rubber particles in the high-impact polystyrene can be obtained by staining an ultrathin section of the high-impact polystyrene as a target with an aqueous solution of osmium tetroxide, photographing the sample prepared by the section using a transmission electron microscope, observing the photograph obtained by the section, and obtaining the volume average particle size using the following formula. For example, the volume average particle size of the rubber particles can be calculated using the following formula for about 500 to about 700 rubber particles in the photograph based on the transmission electron microscope.

[0058] Volume average particle size = Σ(ni·Di 4 ) / Σ(ni·Di 3 )

[0059] In this formula, ni represents the number of rubber particles having a particle size Di. The particle size Di was measured at intervals of 0.1 μm, and when the shape of the rubber particles in the photograph was not circular, the particle size Di was measured as an equivalent circle.

[0060] In addition, as a manufacturing process of high-impact polystyrene having a volume average particle size of 0.1 to 2.0 μm, a known method described in, for example, Japanese Patent Laid-Open No. 3-28210 can be used. Commercially available products of high-impact polystyrene having the above volume average particle size include HT478 manufactured by PS JAPAN, XL1 and XL4 manufactured by Toyo Styrene Corporation, etc.

[0061] As a melt flow rate (MFR) reflecting the molecular weight of the styrene resin (b), the measured value under the conditions of a temperature of 200°C and a load of 5 kg is preferably in the range of 0.5 to 15 g / 10 minutes, and the measured value is more preferably in the range of 1.0 to 10 g / 10 minutes. In addition, the weight average molecular weight (Mw) of the styrene resin (b) is, for example, preferably 50,000 or more, more preferably 100,000 or more, and further preferably 150,000 or more. In addition, the upper limit of the Mw of the styrene resin (b) is, for example, preferably 500,000 or less, more preferably 400,000 or less, and further preferably 300,000 or less. It should be noted that the Mw of the styrene resin (b) can be measured by a measurement method such as size exclusion chromatography.

[0062] It should be noted that the method for producing the styrene resin (b) is not particularly limited, and a known method can be used. For example, the styrene resin (b) can be produced by methods such as emulsion polymerization, solution polymerization, suspension polymerization, or bulk polymerization. In addition, as the styrene resin (b), one styrene resin can be used alone, or two or more styrene resins can be used in combination.

[0063] The styrene resin (b) is contained in the polyphenylene ether-containing resin (A) at a lower content than the polyphenylene ether resin (a) as the main component thereof. In order to improve the flame retardancy and other properties of the PPE resin composition (Z), the content of the styrene resin (b) is set in consideration of the balance between the content of the styrene resin (b) and the polyphenylene ether resin (a).

[0064] For example, from the viewpoint of improving the heat resistance, flame retardancy and mechanical strength of the PPE-based resin composition (Z), the content ratio of each of the polyphenylene ether-based resin (a) and the styrene-based resin (b) in 100% by mass of the polyphenylene ether-containing resin (A) is preferably within the above range.

[0065] In the embodiment of the present invention, the impact resistance of the PPE-based resin composition (Z) can be expressed by, for example, the notched Charpy impact strength measured in accordance with ISO-179-1 and ISO-179-2. The notched Charpy impact strength of the PPE-based resin composition (Z) is preferably 9.0 kJ / m at a temperature of 23°C. 2 above.

[0066] In addition, the flame retardancy of the PPE-based resin composition (Z) can be expressed, for example, by a combustion level (V-0, V-1, V-2, etc.), which is determined by a flammability test based on the UL94 standard (hereinafter referred to as the UL94V test). In the present invention, the flame retardancy of the PPE-based resin composition (Z) preferably satisfies V-0 in terms of the combustion level based on the UL94V test.

[0067] [Other resin components]

[0068] Next, other resin components other than the polyphenylene ether resin (a) and the styrene resin (b) among the resin components contained in the polyphenylene ether-containing resin (A) are described in detail. The polyphenylene ether-containing resin (A) may contain other resin components other than the polyphenylene ether resin (a) and the styrene resin (b) within the range that the effect of improving the properties such as the tracking resistance, flame retardancy and impact resistance of the PPE-based resin composition (Z) according to the embodiment of the present invention is not impaired.

[0069] Specifically, the other resin components include, for example, thermoplastic resins and thermosetting resins. Examples of the thermoplastic resins include, for example, polyamide resins, polyester resins, polyphenylene sulfide resins, liquid crystal polyester resins, polycarbonate resins, polyacetal resins, polyacrylonitrile resins, acrylic resins, polyethylene resins, polypropylene copolymer resins, and other olefin resins. Examples of the thermosetting resins include, for example, epoxy resins, melamine resins, silicone resins, and the like.

[0070] The polyphenylene ether-containing resin (A) may contain two or more thermoplastic resins, two or more thermosetting resins, or a combination of two or more of these thermoplastic resins and thermosetting resins as the other resin components. In addition, the content of the other resin components in 100% by mass of the polyphenylene ether-containing resin (A) is preferably 5% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

[0071] [Inorganic filler (c)]

[0072] Next, the inorganic filler (c) described in the embodiment of the present invention is described in detail. The inorganic filler (c) is a component constituting the PPE-based resin composition (Z) described in the embodiment of the present invention, and is contained in the PPE-based resin composition (Z) mainly for the purpose of improving the mechanical strength of the PPE-based resin composition (Z).

[0073] Examples of such inorganic fillers (c) include glass fibers, glass flakes, glass beads, milled fibers, alumina fibers, carbon fibers, aramid fibers, titanium oxide, boron nitride, potassium titanate whiskers, silica, mica, talc, wollastonite, etc. Among these, the inorganic filler (c) preferably contains at least one selected from glass fibers, mica, and talc, and is particularly preferably glass fibers, from the perspective of having a high effect of improving the mechanical strength of the PPE-based resin composition (Z) relative to the amount added.

[0074] The inorganic filler (c) is not particularly limited in shape or the like. The inorganic filler (c) may be used alone or in combination of two or more.

[0075] Glass fibers suitable for use as the inorganic filler (c) are fibers having an average diameter of 20 μm or less. In addition, from the viewpoint of further improving the physical property balance (heat-resistant rigidity, impact strength) of the PPE-based resin composition (Z) and further reducing the molding warpage of the PPE-based resin composition (Z), the glass fibers are particularly preferably fibers having an average diameter of 1 to 15 μm.

[0076] The length of the glass fiber as the inorganic filler (c) is not particularly limited, and can be selected from long fiber types (rovings) or short fiber types (chopped strands) and the like. The number of bundled roots of the glass fiber in this case is preferably about 100 to 5000. In addition, if the average length of the glass fiber contained in the PPE-based resin composition (Z) after mixing is more than 0.1 mm, the inorganic filler (c) can be a crushed product of a strand of so-called ground fiber or glass powder, or a sliver of a continuous monofilament. In addition, the composition of the raw glass of the glass fiber as the inorganic filler (c) can be an alkali-free composition. As the glass fiber, for example, E glass, C glass, S glass, etc. can be listed. Among these, as the inorganic filler (c), E glass is preferred.

[0077] In addition, as inorganic filler (c), in order to improve the adhesion with resin, it is more preferred to use a material that has been surface treated using a surface treatment agent such as a coupling agent. In the case of using an inorganic filler (c) that has been surface treated, there is a tendency for durability, moisture and heat resistance, hydrolysis resistance, and excellent thermal shock resistance. As a surface treatment agent, any known substance can be used, specifically, various coupling agents such as aminosilane, epoxysilane, allylsilane, vinylsilane, and titanate can be preferably listed. Among these, preferably aminosilane, epoxysilane, and vinylsilane surface treatment agents, specifically, as preferred examples, such as γ-aminopropyl triethoxysilane, γ-aminopropyl trimethoxysilane, and γ-(2-aminoethyl) aminopropyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, vinyl trichlorosilane, vinyl triethoxysilane, and γ-methacryloxypropyl trimethoxysilane can be listed. These silane compounds can be used alone or in combination. Furthermore, as the inorganic filler (c), a material surface-treated with a lubricant such as a fatty acid amide compound, silicone oil, an antistatic agent such as a quaternary ammonium salt, an epoxy resin, a carbamate resin, or a mixture of a resin having a film-forming ability and a heat stabilizer, a flame retardant, etc., can be used on the basis of the above-mentioned surface treatment agent as required.

[0078] In the PPE resin composition (Z) according to the embodiment of the present invention, when two or more inorganic fillers (c) are used, the content of glass fiber is preferably 25% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more in 100% by mass of the inorganic filler (c) mixed. By using glass fiber within this range as a component of the inorganic filler (c), the mechanical strength of the PPE resin composition (Z) can be effectively improved.

[0079] In the PPE resin composition (Z) described in the embodiment of the present invention, the content of the inorganic filler (c) is 5 parts by mass or more, preferably 8 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 12 parts by mass or more relative to 100 parts by mass of the resin (A) containing polyphenylene ether. As described above, by setting the lower limit of the content of the inorganic filler (c) contained in the PPE resin composition (Z) to 5 parts by mass or more, the mechanical strength of the PPE resin composition (Z) can be improved, and then, the improvement of dimensional accuracy and the reduction of the difference in thermal expansion coefficient with other materials (metal materials, etc.) can be achieved. In addition, the content of the inorganic filler (c) is 25 parts by mass or less, preferably 23 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 18 parts by mass or less relative to 100 parts by mass of the resin (A) containing polyphenylene ether. As described above, by setting the upper limit of the content of the inorganic filler (c) contained in the PPE-based resin composition (Z) to 25 parts by mass or less, the PPE-based resin composition (Z) tends to have higher tracking resistance.

[0080] In an embodiment of the present invention, the mechanical strength of the PPE-based resin composition (Z) can be expressed by, for example, tensile strength, flexural strength, and flexural modulus. The tensile strength of the PPE-based resin composition (Z) is measured in accordance with ISO-527. The flexural strength and flexural modulus of the PPE-based resin composition (Z) are measured in accordance with ISO-178.

[0081] When the content of the inorganic filler (c) is less than 5 parts by mass, the effect of improving the mechanical strength by the inorganic filler (c) cannot be obtained. In addition, when the content of the inorganic filler (c) exceeds 25 parts by mass, the tracking resistance of the PPE-based resin composition (Z) is significantly deteriorated.

[0082] [Phosphorus flame retardant (d)]

[0083] Next, the phosphorus flame retardant (d) used in the PPE resin composition (Z) described in the embodiment of the present invention is described in detail. In the PPE resin composition (Z), in addition to the above-mentioned polyphenylene ether-containing resin (A) and the inorganic filler (c), a phosphorus flame retardant (d) is also contained. The phosphorus flame retardant (d) is used to give the PPE resin composition (Z) the flame retardancy required according to the use of the PPE resin composition (Z). By containing the phosphorus flame retardant (d), the PPE resin composition (Z) has better flame retardancy.

[0084] Phosphorus flame retardant (d) has good compatibility with the above-mentioned polyphenylene ether resin (a), therefore, it is preferred as a flame retardant applied to PPE resin composition (Z). As phosphorus flame retardant (d), for example, ethyl phosphinate metal salt, diethyl phosphinate metal salt, phosphoric acid ester, condensed phosphoric acid ester, phosphazene compound, etc. can be listed. Among these, phosphoric acid ester, condensed phosphoric acid ester, phosphazene compound, more preferably phosphoric acid ester, condensed phosphoric acid ester. In addition, as phosphorus flame retardant (d), one phosphorus flame retardant can be used alone, preferably in combination with two or more phosphorus flame retardants with different compositions. In particular, it is more preferred to use two or more selected from phosphoric acid ester and condensed phosphoric acid ester in combination.

[0085] For example, the phosphorus-based flame retardant (d) is particularly preferably a phosphate-based flame retardant represented by the following general formula (3).

[0086]

[0087] In the general formula (3), R 1 , R 2 , R 3 , R 4 Each independently represents an aryl group. The aryl group may be substituted or unsubstituted. X represents a divalent aromatic group. The divalent aromatic group may or may not have a substituent. n represents an integer of 0 to 5.

[0088] As R 1 , R 2 , R 3 , R 4 The aryl groups represented by R include, for example, phenyl and naphthyl. In addition, as the divalent aromatic group represented by X, for example, phenylene, naphthylene, or a group derived from bisphenol can be listed. 1 , R 2 , R 3 , R 4 The substituents of each of X include, for example, alkyl, alkoxy, hydroxyl, etc. In addition, when the integer n is 0, the phosphate flame retardant represented by the general formula (3) is a phosphate ester. When the integer n is any one of 1 to 5, the phosphate flame retardant represented by the general formula (3) is a condensed phosphate ester. The condensed phosphate ester may be a mixture.

[0089] As such phosphate flame retardants, for example, triphenyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, or their substitutes, condensates, etc. can be cited. As commercially available products of such phosphate flame retardants, for example, "TPP" (triphenyl phosphate), "CR733S" (resorcinol bis(diphenyl phosphate)), "CR741" (bisphenol A bis(diphenyl phosphate)), "PX-200" (resorcinol bis(di(xylyl) phosphate)), "FP-900L" (biphenyl-4,4'-diol bis(diphenyl phosphate)) manufactured by Daihachi Chemical Industry Co., Ltd. are suitable and can be easily obtained.

[0090] The lower limit of the content of the phosphorus flame retardant (d) contained in the PPE resin composition (Z) is 15 parts by mass or more, preferably 16 parts by mass or more, relative to 100 parts by mass of the resin (A) containing polyphenylene ether. As described above, by setting the lower limit of the content of the phosphorus flame retardant (d) contained in the PPE resin composition (Z) to 15 parts by mass or more, the flame retardancy of the PPE resin composition (Z) can be improved. In addition, the upper limit of the content of the phosphorus flame retardant (d) is 27 parts by mass or less, preferably 26 parts by mass or less, and more preferably 25 parts by mass or less, relative to 100 parts by mass of the resin (A) containing polyphenylene ether. As described above, by setting the upper limit of the content of the phosphorus flame retardant (d) contained in the PPE resin composition (Z) to 27 parts by mass or less, there is a tendency that the heat resistance and impact resistance of the PPE resin composition (Z) are no longer impaired.

[0091] Specifically, when the PPE resin composition (Z) contains a polyolefin resin (e) described later for the purpose of improving the tracking resistance, the flame retardancy of the PPE resin composition (Z) may be reduced due to the easy combustion of the polyolefin resin (e). In contrast, by making the PPE resin composition (Z) contain the phosphorus flame retardant (d) in the above-mentioned content, the reduction in flame retardancy caused by the polyolefin resin (e) can be suppressed, and the flame retardancy of the PPE resin composition (Z) can be improved.

[0092] It should be noted that, as described above, the flame retardancy of the PPE-based resin composition (Z) is represented by the combustion level determined by the UL94V test. The flame retardancy of the PPE-based resin composition (Z) can be improved to a degree that satisfies V-0 in terms of the combustion level by containing the above-mentioned phosphorus-based flame retardant (d).

[0093] When the content of the phosphorus flame retardant (d) is less than 15 parts by mass, it is difficult to impart flame retardancy to the PPE resin composition (Z) even if the PPE resin composition (Z) contains the phosphorus flame retardant (d). In addition, when the content of the phosphorus flame retardant (d) exceeds 27 parts by mass, the impact resistance and heat resistance of the PPE resin composition (Z) may be reduced.

[0094] When the content of the inorganic filler (c) is 12 parts by mass or more based on 100 parts by mass of the polyphenylene ether-containing resin (A), the content of the phosphorus-based flame retardant (d) is preferably 18 to 27 parts by mass in order to impart flame retardancy to the PPE-based resin composition (Z).

[0095] [Polyolefin resin (e)]

[0096] Next, a polyolefin resin (e), which is one component constituting the PPE resin composition (Z) according to an embodiment of the present invention, is described in detail. The polyolefin resin (e) is a polyolefin resin having a skeleton derived from ethylene, and is contained in the PPE resin composition (Z) for the purpose of improving the tracking resistance and impact resistance of the PPE resin composition (Z).

[0097] In the embodiment of the present invention, "polyolefin resin having a skeleton derived from ethylene" refers to a polyolefin resin generated by a polymerization reaction of at least one monomer containing ethylene. That is, the polyolefin resin (e) is a homopolymer or copolymer containing at least ethylene as a monomer unit. For example, when the polyolefin resin (e) is a homopolymer, polyethylene can be listed as the homopolymer. When the polyolefin resin (e) is a copolymer, copolymers of ethylene and monomers other than ethylene can be listed as the copolymer, specifically, ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-propylene-butene copolymers, etc. can be listed.

[0098] Here, in the resin composition containing a polyolefin resin having a skeleton derived from ethylene, a nucleating agent such as a metal salt of an aromatic carboxylic acid or talc is sometimes mixed for the purpose of improving the crystallinity of the polyolefin resin. However, when a nucleating agent is mixed into a polyolefin resin, the tracking resistance of the resin composition containing the polyolefin resin may deteriorate. Therefore, the polyolefin resin (e) described in an embodiment of the present invention is preferably a polyolefin resin that does not contain a nucleating agent.

[0099] The melt flow rate (hereinafter appropriately referred to as MFR) of the polyolefin resin (e) is measured in accordance with JIS K7210. For example, under the measurement conditions of a temperature of 190°C and a load of 2.16 kg, the lower limit of the MFR is preferably 0.5 g / 10 minutes or more, more preferably 0.8 g / 10 minutes or more, further preferably 1.0 g / 10 minutes or more, and particularly preferably 1.2 g / 10 minutes or more. When the MFR of the polyolefin resin (e) under the above measurement conditions is less than 0.5 g / 10 minutes, the processability (moldability) and flame retardancy of the PPE-based resin composition (Z) containing the polyolefin resin (e) are sometimes reduced. For example, it can be considered that the reduction in flame retardancy in this case occurs because the dispersibility of the polyolefin resin (e) having an MFR of less than 0.5 g / 10 minutes in the PPE-based resin composition (Z) is reduced. In addition, from the viewpoint of suppressing the reduction of the mechanical strength of the PPE-based resin composition (Z), the upper limit of the MFR of the polyolefin resin (e) under the above-mentioned measurement conditions is preferably 100 g / 10 minutes or less, more preferably 40 g / 10 minutes or less, further preferably 20 g / 10 minutes or less, and particularly preferably 10 g / 10 minutes or less. When the MFR exceeds 100 g / 10 minutes, the mechanical strength and flame retardancy of the PPE-based resin composition (Z) containing the polyolefin resin (e) are sometimes reduced. For example, it can be considered that the reduction in flame retardancy in this case occurs for the following reasons: the viscosity difference between the polyolefin resin (e) having an MFR exceeding 100 g / 10 minutes and the components contained in the PPE-based resin composition (Z) is large, and therefore, the dispersion state of the polyolefin resin (e) in the PPE-based resin composition (Z) changes.

[0100] In addition, in this embodiment, as a polyolefin resin (e), a single polyolefin resin may be used alone, or two or more polyolefin resins may be blended and used.

[0101] In the PPE resin composition (Z) described in the embodiment of the present invention, the content of the polyolefin resin (e) is 0.3 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and further preferably 3 parts by mass or more, relative to 100 parts by mass of the resin (A) containing polyphenylene ether. In addition, the content of the polyolefin resin (e) is 7 parts by mass or less, preferably 6 parts by mass or less, more preferably 5.5 parts by mass or less, and further preferably 5 parts by mass or less, relative to 100 parts by mass of the resin (A) containing polyphenylene ether. By making the PPE resin composition (Z) contain a polyolefin resin (e) in a content within this range, the flame retardancy of the PPE resin composition (Z) will not be impaired, and the tracking resistance can be improved.

[0102] The tracking resistance of the PPE resin composition (Z) can be expressed by a comparative tracking index (hereinafter referred to as a CTI value), which is an index indicating the ease of tracking of an insulator. The CTI value of the PPE resin composition (Z) is measured in accordance with IEC60112 and can be increased to a prescribed value or more by containing the above-mentioned polyolefin resin (e). For example, the CTI value of the PPE resin composition (Z) is preferably 250V or more.

[0103] When the content of the polyolefin resin (e) is less than 0.3 parts by mass, the effect of improving the tracking resistance and impact resistance by using the polyolefin resin (e) cannot be obtained. That is, the CTI value and impact resistance of the PPE-based resin composition (Z) will not be improved to the target value. In addition, when the content of the polyolefin resin (e) exceeds 7 parts by mass, the mechanical strength of the PPE-based resin composition (Z) is reduced. Furthermore, the polyolefin resin (e) is a resin that is easily flammable, and therefore, the flame retardancy of the PPE-based resin composition (Z) will also be impaired.

[0104] On the other hand, the polyolefin resin (e) can improve the impact resistance of the PPE-based resin composition (Z) by being dispersed in the polyphenylene ether-containing resin (A). It is believed that the effect of improving the impact resistance is because the polyolefin resin (e) itself has high impact resistance and the polyolefin resin (e) is easily dispersed in the PPE-based resin composition (Z) in a state suitable for absorbing impact.

[0105] [Tracking resistance improver (f)]

[0106] Next, the tracking resistance improver (f) used in the PPE resin composition (Z) described in the embodiment of the present invention is described in detail. The PPE resin composition (Z) contains the above-mentioned polyphenylene ether-containing resin (A), inorganic filler (c), phosphorus flame retardant (d) and polyolefin resin (e), and also contains a tracking resistance improver (f). The tracking resistance improver (f) is a component mixed into the PPE resin composition (Z) for the purpose of improving the tracking resistance of the PPE resin composition (Z).

[0107] Examples of such tracking resistance improvers (f) include alkaline earth metal salts, metal hydroxides, nitrogen-containing compounds, inorganic acid metal compounds, salts of aminotriazine compounds, organic acids or inorganic acid salts of the aminotriazine compounds, layered double hydroxides, metal sulfates, metal sulfides, etc. Among these, the tracking resistance improver (f) preferably contains at least one selected from the group consisting of alkaline earth metal salts, metal hydroxides, nitrogen-containing compounds, inorganic acid metal compounds, and layered double hydroxides.

[0108] Examples of the alkaline earth metal salt include carbonates such as calcium carbonate, phosphates (hydrogen) such as calcium hydrogen phosphate, etc. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, aluminum oxide hydrate (boehmite), etc. Examples of the inorganic acid metal compound include (hydrous) boric acid metal salts, (hydrous) stannate metal salts, etc. Examples of the (hydrous) boric acid metal salt include (hydrous) zinc borate, (hydrous) calcium borate, (hydrous) aluminum borate, etc. Examples of the (hydrous) stannate metal salt include (hydrous) zinc stannate, etc.

[0109] In addition, examples of the nitrogen-containing compound include aminotriazine compounds exemplified by melamine condensates such as melamine, guanamine, melam, and melem. Examples of organic or inorganic acid salts of the aminotriazine compound include cyanurates such as melamine cyanurate, phosphates such as polyphosphate melamine, and the like. Examples of the layered double hydroxide include hydrotalcite, and the like. Examples of the metal sulfate include calcium sulfate, magnesium sulfate, and barium sulfate, and the like. Examples of the metal sulfide include zinc sulfide, molybdenum sulfide, and tungsten sulfide, and the like.

[0110] As the tracking resistance improver (f), an alkaline earth metal salt is more preferred. Among the alkaline earth metal salts, the tracking resistance improver (f) is particularly preferably calcium carbonate.

[0111] When the tracking resistance improver (f) is in the state of a raw material (the state before being included in the PPE-based resin composition (Z)), the average particle size of the primary particles of the tracking resistance improver (f) is preferably 0.1 to 15 μm, and more preferably 0.15 to 5 μm. The average particle size of the primary particles of the tracking resistance improver (f) can be obtained by observing using a scanning electron microscope (SEM) and taking the arithmetic average of the average particle size of the primary particle size of the particles in the photographed photograph. When the average particle size of the primary particles of the tracking resistance improver (f) is a particle of 0.1 μm or more, aggregation can be prevented, and dispersion becomes good during melt kneading. In addition, when the average particle size of the primary particles is a particle of 15 μm or less, there is a tendency not to reduce the impact resistance of the PPE-based resin composition (Z) and to improve the tracking resistance.

[0112] As the tracking resistance improver (f), one type of tracking resistance improver may be used alone, or two or more types of tracking resistance improvers may be used in combination.

[0113] In addition, the tracking resistance improver (f) may be surface treated. The surface treatment of the tracking resistance improver (f) is not particularly limited, and may be, for example, a surface treatment based on fatty acids, resin acids, silicic acid, phosphoric acid, silane coupling agents, alkyl aryl sulfonic acids or their salts, etc. As the fatty acid, saturated or unsaturated fatty acids having 6 to 31 carbon atoms may be listed, and saturated or unsaturated fatty acids having 12 to 28 carbon atoms may be preferably listed. Among them, from the viewpoint of dispersibility and operability during manufacture, a tracking resistance improver (f) surface treated with a fatty acid is preferred. When calcium carbonate surface treated with a fatty acid is used as the tracking resistance improver (f), the tracking resistance improver (f) is more evenly dispersed in the polyphenylene ether-containing resin (A), thereby making the tracking resistance of the PPE-based resin composition (Z) more excellent.

[0114] In addition, the lower limit of the content of the tracking resistance improver (f) contained in the PPE-based resin composition (Z) is 3 parts by mass or more relative to 100 parts by mass of the resin (A) containing polyphenylene ether. The upper limit of the content of the tracking resistance improver (f) is 20 parts by mass or less relative to 100 parts by mass of the resin (A) containing polyphenylene ether. By making the PPE-based resin composition (Z) contain the tracking resistance improver (f) in a content within this range, the tracking resistance of the PPE-based resin composition (Z) can be improved.

[0115] The tracking resistance improver (f) suppresses the generation of carbonized components and promotes the volatilization of the carbonized components by its own endothermic dilution effect of dehydration or decomposition, and as a result, can also improve the tracking resistance of the PPE-based resin composition (Z) alone. On this basis, the tracking resistance improver (f) can assist the flame retardancy of the PPE-based resin composition (Z) based on the phosphorus-based flame retardant (d), and thus, there is a tendency to synergistically improve the flame retardancy of the PPE-based resin composition (Z) with the phosphorus-based flame retardant (d).

[0116] When the content of the tracking resistance improver (f) is less than 3 parts by mass, even if the PPE resin composition (Z) contains the tracking resistance improver (f), the tracking resistance of the PPE resin composition (Z) may not be improved. In addition, when the content of the tracking resistance improver (f) exceeds 20 parts by mass, the mechanical properties such as rigidity and impact resistance, heat resistance and fluidity of the PPE resin composition (Z) may be reduced.

[0117] [Phosphorus stabilizer (g)]

[0118] Next, the phosphorus-based stabilizer (g) used in the PPE-based resin composition (Z) described in the embodiment of the present invention is described in detail. The PPE-based resin composition (Z) contains the above-mentioned polyphenylene ether-containing resin (A), inorganic filler (c), phosphorus-based flame retardant (d), polyolefin resin (e) and tracking resistance improver (f), and also contains a phosphorus-based stabilizer (g). The phosphorus-based stabilizer (g) is a component contained in the PPE-based resin composition (Z) for the purpose of improving the thermal stability of the PPE-based resin composition (Z) during melt mixing in the manufacturing and molding processes and during use, and imparting flame retardancy to the PPE-based resin composition (Z).

[0119] Examples of the phosphorus stabilizer (g) include phosphite compounds and phosphonite compounds. These compounds may be used alone or in combination of two or more as the phosphorus stabilizer (g). The phosphorus stabilizer (g) preferably includes at least one of a phosphite compound and a phosphonite compound.

[0120] Examples of the phosphite compounds include phosphites, etc. Specific examples of the phosphite compounds include tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol-diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, 4,4'-butylidene-bis-(3-methyl-6-tert-butylphenyl-ditridecyl)phosphite, 1,1,3-tris(2-methyl-4-ditridecylphosphite-5-tert-butyl-phenyl)butane, tris(mixed monononylphenyl and dinonylphenyl)phosphite, tris(nonylphenyl)phosphite, and 4,4'-isopropylidenebis(phenyl-dialkylphosphite). Among these, tris(2,4-di-tert-butylphenyl)phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite are preferred.

[0121] Specific examples of the phosphite-based compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphite, tetrakis(2,5-di-tert-butylphenyl)-4,4'-biphenylene diphosphite, tetrakis(2,3,4-trimethylphenyl)-4,4'-biphenylene diphosphite, tetrakis(2,3-dimethyl-5-ethylphenyl)-4,4'-biphenylene diphosphite, tetrakis(2,6-di-tert-butyl-5-ethylphenyl)-4,4'-biphenylene diphosphite, tetrakis(2,3,4-tributylphenyl)-4,4'-biphenylene diphosphite, and tetrakis(2,4,6-tri-tert-butylphenyl)-4,4'-biphenylene diphosphite. Among these, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphite is preferred.

[0122] The lower limit of the content of the phosphorus-based stabilizer (g) contained in the PPE-based resin composition (Z) is 0.5 parts by mass or more, preferably 1 part by mass or more, and more preferably 1.2 parts by mass or more, relative to 100 parts by mass of the resin (A) containing polyphenylene ether. In addition, the upper limit of the content of the phosphorus-based stabilizer (f) is 3 parts by mass or less, preferably 2.5 parts by mass or less, and more preferably 2 parts by mass or less, relative to 100 parts by mass of the resin (A) containing polyphenylene ether. By making the PPE-based resin composition (Z) contain a phosphorus-based stabilizer (g) in an amount within this range, the thermal stability of the PPE-based resin composition (Z) during melt mixing and use in the manufacturing and molding processes can be improved, and the flame retardancy of the PPE-based resin composition (Z) can be improved.

[0123] In addition, the total content of the polyphenylene ether resin (a), styrene resin (b), inorganic filler (c), phosphorus flame retardant (d), polyolefin resin (e), tracking resistance improver (f) and phosphorus stabilizer (g) contained in the PPE resin composition (Z) is preferably 95% by mass or more, more preferably 97% by mass or more, further preferably 98% by mass or more, and particularly preferably 99% by mass or more relative to 100% by mass of the PPE resin composition (Z). By setting the total content within the above range, a PPE resin composition (Z) having better tracking resistance, flame retardancy and impact resistance can be obtained.

[0124] [Mass Ratio of Polyolefin Resin to Phosphorus Component in PPE-Based Resin Composition]

[0125] Next, the mass ratio of the polyolefin resin (e) to the phosphorus component in the PPE resin composition (Z) according to the embodiment of the present invention is described in detail. As described above, the PPE resin composition (Z) contains components such as the polyolefin resin (e). In addition, the PPE resin composition (Z) contains a phosphorus component. The mass ratio (E / P) of the polyolefin resin (e) to the phosphorus component in this PPE resin composition (Z) is 0.2 to 2.65.

[0126] In detail, the PPE resin composition (Z) contains the above-mentioned phosphorus flame retardant (d) and phosphorus stabilizer (g). That is, the phosphorus component in the PPE resin composition (Z) includes at least the phosphorus component in the phosphorus flame retardant (d) and the phosphorus component in the phosphorus stabilizer (g). The above-mentioned mass ratio (E / P) in this PPE resin composition (Z) is the ratio of the content mass (E) of the polyolefin resin (e) contained in the PPE resin composition (Z) to the total content mass (P) of the phosphorus component (= (E) / (P)). The polyolefin resin (e), the phosphorus flame retardant (d) and the phosphorus stabilizer (g) are contained in the PPE resin composition (Z) in a manner that satisfies the content range relative to 100 parts by mass of the above-mentioned polyphenylene ether-containing resin (A) and the range of the above-mentioned mass ratio (E / P).

[0127] It should be noted that the mass (P) of the phosphorus component in the PPE-based resin composition (Z) can be quantified by, for example, ICP emission spectrometry. Specifically, the PPE-based resin composition (Z) is subjected to wet acid decomposition, and after filtering out the inorganic filler (c), the constant volume solution is introduced into an ICP emission spectrometry device to measure the phosphorus concentration. According to the value of the measured phosphorus concentration, the mass (P) of the phosphorus component of the PPE-based resin composition (Z) can be calculated. As an ICP emission spectrometry device, for example, Ultima2C manufactured by Horiba, Ltd. can be used. In addition, the mass (P) of the phosphorus component can be the following value: by analyzing the molecular structure, the mass of the phosphorus component in the phosphorus-based flame retardant (d) and the mass of the phosphorus component in the phosphorus-based stabilizer (g) are respectively derived, and the mass of each derived phosphorus component is added together to obtain the value. For example, the mass content of the phosphorus component in the phosphorus stabilizer (g) can be derived by deriving the mass ratio of phosphorus atoms relative to the molecular weight of the phosphorus stabilizer (g) based on the analysis results of the molecular structure, and multiplying the derived mass ratio by the amount of phosphorus stabilizer (g) added to derive the mass content. Alternatively, when the phosphorus stabilizer (g) is a commercially available product, the mass content of the phosphorus component in the phosphorus stabilizer (g) is derived by multiplying the mass ratio of the phosphorus component set by the commercial product by the amount of phosphorus stabilizer (g) added. It should be noted that the mass content of the phosphorus component in the phosphorus flame retardant (d) can also be derived in the same manner as the case of the above-mentioned phosphorus stabilizer (g).

[0128] [additive]

[0129] Next, the additives used in the PPE resin composition (Z) described in the embodiment of the present invention are described in detail. In the PPE resin composition (Z), in addition to the above-mentioned polyphenylene ether-containing resin (A), inorganic filler (c), phosphorus flame retardant (d), polyolefin resin (e), tracking resistance improver (f) and phosphorus stabilizer (g), other additives may also be contained within the scope of the present invention. As such additives, for example, heat stabilizers, ultraviolet absorbers, antioxidants, weather resistance improvers, foaming agents, lubricants, plasticizers, flow improvers, dispersants, conductive agents, antistatic agents, colorants, etc., other than phosphorus stabilizers (g) can be listed.

[0130] Among the above-mentioned additives, examples of heat stabilizers other than the phosphorus stabilizer (g) (hereinafter referred to as stabilizer (h)) include hindered phenol compounds, sulfur compounds, zinc oxide, etc. These compounds may be used alone or in combination of two or more as the stabilizer (h).

[0131] Specific examples of hindered phenol compounds include n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 1,6-hexanediol-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate], pentaerythritol-tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol, 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[ 5,5〕undecane, triethylene glycol-bis〔3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate〕, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tri(3',5'-di-tert-butyl-4'-hydroxybenzyl)benzene, 2,2-thiodiethylenebis〔3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate〕, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic amide), etc. Among these, preferred are n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 1,6-hexanediol-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methylphenol, and 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane.

[0132] Specific examples of sulfur compounds include, for example, didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate), pentaerythritol tetrakis (3-tetradecylthiopropionate), pentaerythritol tetrakis (3-tridecylthiopropionate), thiobis (N-phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, trilauryl trithiophosphite, etc. Among these, thioether antioxidants having a thioether structure receive oxygen from an oxidized substance and are reduced, and therefore can be suitably used as a stabilizer (h). The lower limit of the molecular weight of the sulfur compound is usually 200 or more, preferably 500 or more. The upper limit of the molecular weight of the sulfur compound is usually 3000 or less.

[0133] As zinc oxide, for example, zinc oxide having an average particle size of 0.02 to 1 μm is preferred, and zinc oxide having an average particle size of 0.08 to 0.8 μm is more preferred.

[0134] For example, when the PPE resin composition (Z) contains a stabilizer (h), the content of the stabilizer (h) is preferably 0.001 to 1 part by mass, more preferably 0.01 to 0.7 parts by mass, and further preferably 0.02 to 0.5 parts by mass relative to 100 parts by mass of the polyphenylene ether-containing resin (A). By setting the lower limit of the content of the stabilizer (h) to 0.001 parts by mass or more, the effect of improving the thermal stability of the PPE resin composition (Z) can be fully obtained. In addition, by setting the upper limit of the content of the stabilizer (h) to 1 part by mass or less, mold contamination that occurs when the PPE resin composition (Z) is molded, a reduction in the mechanical strength of the PPE resin composition (Z), etc. can be prevented.

[0135] Among the above-mentioned additives, examples of colorants include black pigments (i), white pigments, and dyes. The PPE-based resin composition (Z) may contain at least one colorant for the purpose of coloring.

[0136] As black pigment (i), for example, carbon black, carbon nanotubes or their thermoplastic resin masterbatch can be listed. When the PPE resin composition (Z) contains black pigment (i), the content of black pigment (i) is preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less, further preferably 1.0 parts by mass or less, and particularly preferably 0.5 parts by mass or less relative to 100 parts by mass of the resin (A) containing polyphenylene ether. The lower limit of the content of the black pigment (i) is not particularly limited as long as the color of the PPE resin composition (Z) can be adjusted, and is preferably 0.01 parts by mass or more. By making the PPE resin composition (Z) contain a black pigment (i) with a content within a range, it is possible to adjust the color without damaging the tracking resistance of the PPE resin composition (Z).

[0137] As white pigment, for example, titanium oxide, zinc sulfide, etc. can be cited. When the PPE resin composition (Z) contains a white pigment, the content of the white pigment is preferably 7.0 parts by mass or less, more preferably 4.0 parts by mass or less, further preferably 3.0 parts by mass or less, and particularly preferably 2.0 parts by mass or less relative to 100 parts by mass of the resin (A) containing polyphenylene ether. The lower limit of the content of the white pigment is not particularly limited as long as the coloring of the PPE resin composition (Z) can be performed, and is preferably 0.01 parts by mass or more. By making the PPE resin composition (Z) contain a white pigment in a content within this range, it is possible to perform coloring without damaging the mechanical strength of the PPE resin composition (Z).

[0138] The PPE resin composition (Z) may contain one of the above-mentioned additives, or may contain two or more additives. The PPE resin composition (Z) can effectively exert the functions of each additive contained. For example, when a weather resistance improver and a lubricant are mixed in the PPE resin composition (Z), there is a tendency that the weather resistance of the PPE resin composition (Z) and the demolding property from the mold during injection molding are improved.

[0139] [Method for producing PPE-based resin composition (Z)]

[0140] Next, the method for producing the PPE resin composition (Z) described in the embodiment of the present invention is described in detail. The method for producing the PPE resin composition (Z) is not limited to a specific method, and a known method can be used. As the production method, for example, the following method can be cited: melt-kneading the above-mentioned polyphenylene ether-containing resin (A), inorganic filler (c), phosphorus flame retardant (d), polyolefin resin (e), tracking resistance improver (f) and phosphorus stabilizer (g), etc., and various components mixed as needed by a mixer, and then cooling and solidifying the melt-kneading method; adding the above-mentioned various components to an appropriate solvent, mixing the dissolved components with each other or the dissolved components with the insoluble components in a suspended state, etc. Solution mixing method. As the mixer used in the production method, for example, a single-screw mixing extruder, a multi-screw mixing extruder, a Banbury mixer, a roller, a Brabender plastogram, etc. can be cited. Examples of the solvent include hydrocarbons such as hexane, heptane, benzene, toluene, and xylene, and derivatives thereof.

[0141] From the viewpoint of industrial cost, as a method for producing the PPE-based resin composition (Z), a melt-kneading method is preferred. In the melt-kneading method, the kneading temperature and the kneading time can be arbitrarily selected according to conditions such as the desired PPE-based resin composition (Z) and the type of mixer. For example, the kneading temperature is preferably 200 to 350°C, more preferably 220 to 320°C. The kneading time is preferably 20 minutes or less. When the kneading temperature exceeds 350°C, thermal degradation of the polyphenylene ether-based resin (a) or the styrene-based resin (b) contained in the polyphenylene ether-containing resin (A) may occur. As a result, in the molded product of the PPE-based resin composition (Z), a reduction in physical properties or a poor appearance may occur.

[0142] [Molding products]

[0143] Next, the molded article according to the embodiment of the present invention is described in detail. The molded article according to the embodiment of the present invention is a molded article formed from the above-mentioned PPE-based resin composition (Z), which can be manufactured by, for example, molding pellets obtained by granulating the PPE-based resin composition (Z) using various molding methods. In addition, the molded article can also be manufactured by directly molding the PPE-based resin composition (Z) melt-kneaded by a mixer without passing through the above-mentioned pellets.

[0144] The molding method of the PPE-based resin composition (Z) is not limited to a specific method, and a known method can be used. For example, various molding methods such as injection molding, injection compression molding, hollow molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, and press molding can be cited as molding methods of the PPE-based resin composition (Z).

[0145] The molded product manufactured by the above-mentioned molding method is formed by the PPE-based resin composition (Z) described in the embodiment of the present invention, and therefore has the excellent properties of the various components contained in the PPE-based resin composition (Z). In particular, the molded product has high flame retardancy achieved by polyphenylene ether resin (a), phosphorus flame retardant (d) and phosphorus stabilizer (g), high mechanical strength achieved by inorganic filler (c), and high tracking resistance achieved by polyolefin resin (e) and tracking resistance improver (f). Among them, the impact resistance of the molded product is easy to reach the target height by the combination of polyphenylene ether resin (a) and polyolefin resin (e). The flame retardancy and tracking resistance of the molded product can reach the target height by the above-mentioned control of the mass ratio of polyolefin resin (e) to phosphorus component in the PPE-based resin composition (Z). Furthermore, the molded article can have excellent properties such as high impact resistance and processability, low specific gravity, high dimensional accuracy, hydrolysis resistance, dimensional stability and mechanical properties achieved by the styrene resin (b) in addition to the above properties.

[0146] Since such a molded article has the excellent properties as described above, it can be widely used in various applications such as automobile-related parts, electronic equipment-related parts, and battery-related parts.

[0147] Specifically, as automobile-related parts to which the molded article described in the embodiment of the present invention is applied, for example, automobile outer packaging parts, outer panel parts, interior parts, engine hood parts, etc. can be listed, and more specifically, as automobile outer packaging parts or outer panel parts, bumpers, fenders, door panels, trims, car logos, engine hoods, wheel covers, roofs, spoilers, engine covers, etc. can be listed. As automobile interior parts, instrument panels, console decorative parts, etc. can be listed.

[0148] In addition, as electronic device-related parts to which the molded products described in the embodiments of the present invention are applied, for example, computer parts, computer-related equipment parts, OA equipment parts, television parts, video recorder parts, various disk player parts, housings for these electronic devices, chassis, refrigerator parts, air conditioning equipment parts, liquid crystal projector parts, etc. can be listed.

[0149] Examples of battery-related parts to which the molded article according to the embodiment of the present invention is applied include battery cell cases, electrolytic cells for secondary batteries, fuel cartridges for direct methanol fuel cells, and water pipes for fuel cells.

[0150] In addition, the molded article described in the embodiment of the present invention can also be applied to parts in fields (other fields) other than the above-mentioned automobile-related, electronic equipment-related and battery-related fields. For example, as parts in other fields, water-cooling tanks, boiler outer packaging shells, ink-related parts / components of inkjet printers and chassis, etc. can be listed. In addition to these, the molded article described in the embodiment of the present invention can also be applied to molded bodies such as water pipes and joints, separators for lithium-ion batteries obtained by stretching sheets or films, etc.

[0151] As described above, the PPE resin composition (Z) according to the embodiment of the present invention contains at least a polyphenylene ether-containing resin (A) containing more than 80% by mass of a polyphenylene ether-containing resin (a), and contains, relative to 100 parts by mass of the polyphenylene ether-containing resin (A), 5 to 25 parts by mass of an inorganic filler (c), 15 to 27 parts by mass of a phosphorus-based flame retardant (d), 0.3 to 7 parts by mass of a polyolefin resin (e) having a skeleton derived from ethylene, 3 to 20 parts by mass of a tracking resistance improver (f), and 0.5 to 3 parts by mass of a phosphorus-based stabilizer (g). At this time, the mass ratio of the polyolefin resin (e) in the PPE resin composition (Z) to the phosphorus component is set within a range of 0.2 to 2.65.

[0152] Therefore, the excellent heat resistance achieved by the polyphenylene ether resin (a) can be obtained, and the inorganic filler (c) can be used to strengthen the mechanical strength, and the polyolefin resin (e) can be used to improve the tracking resistance reduced by the inorganic filler (c). On this basis, by the combination of polyphenylene ether resin (a) and polyolefin resin (e), the impact resistance can be improved, and the phosphorus flame retardant (d) can be used to improve the flame retardancy reduced by the polyolefin resin (e), and the tracking resistance improver (f) and the phosphorus stabilizer (g) can be used to stably improve their tracking resistance and flame retardancy. Furthermore, the improvement of these tracking resistance, flame retardancy and impact resistance can be ensured by controlling the mass ratio of the above-mentioned polyolefin resin (e) relative to the phosphorus component. As a result, the PPE resin composition (Z) can have both high tracking resistance and excellent flame retardancy and impact resistance.

[0153] In addition, in the PPE resin composition (Z) according to the embodiment of the present invention, the polyphenylene ether-containing resin (A) contains 85 to 100% by mass of the polyphenylene ether resin (a) and 0 to 15% by mass of the styrene resin (b). Therefore, the excellent heat resistance, processability (moldability) and mechanical properties achieved by the polyphenylene ether resin (a) and the styrene resin (b) can be obtained, and the above-mentioned excellent flame retardancy can be maintained, and the impact resistance can be further improved by using the styrene resin (b).

[0154] In addition, by molding the PPE-based resin composition (Z), a molded product having the effects of the PPE-based resin composition (Z) can be easily obtained. Such a molded product can have various properties (tracking resistance, flame retardancy, impact resistance, etc.) required according to the application by selecting the constituent components of the PPE-based resin composition (Z) as a raw material.

[0155] Example

[0156] Hereinafter, the present invention will be described in more detail with reference to the following examples. It should be noted that the present invention is not to be construed as being limited to the following examples.

[0157] (Examples 1 to 18, Comparative Examples 1 to 9)

[0158] [Components of the polyphenylene ether resin composition]

[0159] The components of the polyphenylene ether-based resin composition (PPE-based resin composition) of Examples 1 to 18 and Comparative Examples 1 to 9 are shown in Tables 1-1 and 1-2.

[0160] Examples 1 to 18 use the polyphenylene ether resin (a), styrene resin (b), inorganic filler (c), phosphorus flame retardant (d), polyolefin resin having a skeleton derived from ethylene (e), tracking resistance improver (f), phosphorus stabilizer (g), other stabilizer (h), and black pigment (i) shown in Table 1-1, respectively, as required. It should be noted that other stabilizer (h) is an example of an additive added to the above-mentioned PPE resin composition (Z) as required, specifically, a heat stabilizer other than the phosphorus stabilizer (g). For example, as the stabilizer (h), a hindered phenol stabilizer can be used.

[0161] Comparative Examples 1 to 9 use the above-mentioned components, the polyolefin resin (x) and the polyethylene wax (y) shown in Table 1-2, respectively, as required. The polyolefin resin (x) is a polyolefin resin that does not have a skeleton derived from ethylene or a polyolefin resin with low fluidity. The polyolefin resin with low fluidity has a skeleton derived from ethylene, but is a polyolefin resin with a low MRF compared to the polyolefin resin (e) used in Examples 1 to 18. The polyolefin resin (x) and the polyethylene wax (y) are used instead of the polyolefin resin (e) having a skeleton derived from ethylene. For example, as a polyolefin resin (x) that does not have a skeleton derived from ethylene, a propylene-butene copolymer that does not contain ethylene in the raw materials of the polymerization reaction is used. As a polyolefin resin (x) with low fluidity, a high-density polyethylene resin with low fluidity is used.

[0162] As shown in Table 1-1, as the polyphenylene ether resin (a), component (a-1) is used. As the styrene resin (b), component (b-1), component (b-2) or component (b-3) is used. As the inorganic filler (c), component (c-1) is used. As the phosphorus flame retardant (d), component (d-1), component (d-2) and component (d-3) are used by appropriately changing the content. As the polyolefin resin (e), component (e-1), component (e-2) or component (e-3) is used. As the tracking resistance improver (f), component (f-1) is used. As the phosphorus stabilizer (g), component (g-1) is used. As the stabilizer (h), component (h-1) is used. As the black pigment (i), component (i-1) is used. In addition, as shown in Table 1-2, as the polyolefin resin (x), component (x-1) or component (x-2) is used. As the polyethylene wax (y), component (y-1) is used.

[0163] The MFR described in Tables 1-1 and 1-2 is a melt flow rate measured in accordance with JIS K7210. The measurement conditions of the MFR are as shown in Tables 1-1 and 1-2, and the temperature is 190° C. The load is not shown in Tables 1-1 and 1-2, but is 2.16 kg.

[0164] [Table 1-1](Table 1-1)

[0165]

[0166] [Table 1-2]

[0167] (Table 1-2)

[0168]

[0169] [Method for producing pellets of PPE-based resin composition]

[0170] In each of Examples 1 to 18 and Comparative Examples 1 to 9, the components shown in Tables 1-1 and 1-2 are mixed in the proportions (parts by mass) shown in Tables 2-1 to 2-3 described below, and a twin-screw extruder (manufactured by Shibaura Machine Co., Ltd.: TEM18SS) is used, the barrel temperature is set to 280°C, the screw speed is set to 300 rpm, and the mixture of the above components is melt-kneaded. Thus, a PPE-based resin composition is prepared. Thereafter, the strands of the PPE-based resin composition are extruded and the extruded strands are cut (granulated) to obtain pellets of the PPE-based resin composition. The pellets of the obtained PPE-based resin composition are used to perform the following evaluations.

[0171] [Evaluation of Tracking Resistance]

[0172] In each of Examples 1 to 18 and Comparative Examples 1 to 9, the tracking resistance of the molded article of the PPE resin composition made using the pellets obtained by the above-mentioned manufacturing method was evaluated. In detail, the pellets of the PPE resin composition based on the above-mentioned manufacturing method were dried at 100°C for 2 hours and then supplied to an injection molding machine (manufactured by Shibaura Machinery Co., Ltd.: EC160NII), and the injection molding machine was used to make a molded article of longitudinal × transverse × thickness = 100mm × 150mm × 3.2mm formed by the PPE resin composition. At this time, as an injection molding condition, the barrel temperature was set to 280°C and the mold temperature was set to 70°C. Using the molded article thus made, the maximum voltage at which the molded article does not suffer from tracking damage, i.e., the CTI value (unit: V), was measured by a measurement method based on IEC60112 (using electrolyte: solution A, number of drops: 50 drops).

[0173] [Evaluation of flame retardancy]

[0174] In each of Examples 1 to 18 and Comparative Examples 1 to 9, the flame retardancy of the test piece of the PPE resin composition prepared using the pellets obtained by the above-mentioned manufacturing method was evaluated. In detail, the pellets of the PPE resin composition based on the above-mentioned manufacturing method were dried at 100°C for 2 hours and then supplied to an injection molding machine (EC75SX manufactured by Shibaura Machinery Co., Ltd.), and the injection molding machine was used to mold a test piece for a flammability test with a longitudinal × transverse × thickness = 125 mm × 13 mm × 1.5 mm formed by the PPE resin composition. At this time, as injection molding conditions, the barrel temperature was set to 280°C and the mold temperature was set to 70°C.

[0175] Next, for the test pieces for the flammability test obtained as above, a vertical flammability test (UL94V test: 1.5mmt) of 5 pieces in a group based on the UL94 standard was carried out twice. In the flame retardancy evaluation of each of Examples 1 to 18 and Comparative Examples 1 to 9, the level based on the vertical flammability test was determined for each group. The levels are classified into V-0, V-1, and V-2 in order from good. In addition, in the flame retardancy evaluation, the maximum burning time is more than 30 seconds, and the result that does not meet any level is judged as NG. It should be noted that when the results (level determination results) obtained by two vertical flammability tests are different from each other, the lower level is adopted as the evaluation result of the flame retardancy.

[0176] [Evaluation of heat resistance]

[0177] In each of Examples 1 to 18 and Comparative Examples 1 to 9, heat resistance was evaluated for a test piece of a PPE resin composition made using pellets obtained by the above-mentioned manufacturing method. Specifically, the pellets of the PPE resin composition based on the above-mentioned manufacturing method were dried at 100°C for 2 hours and then supplied to an injection molding machine (EC75SX manufactured by Shibaura Machine Co., Ltd.), which was injection molded into a type A test piece of ISO-3167:93 (hereinafter referred to as an ISO test piece) in accordance with ISO-15103 using the injection molding machine. At this time, as injection molding conditions, the barrel temperature was set to 280°C and the mold temperature was set to 70°C.

[0178] Next, according to ISO-75-2, the parallel portion of the ISO test piece was machined to produce a short strip-shaped test piece of 80 mm × 10 mm × 4 mm in length × width × thickness. The deflection temperature under load (unit: ° C.) was measured using the test piece under a load of 1.80 MPa.

[0179] [Evaluation of impact resistance]

[0180] In each of Examples 1 to 18 and Comparative Examples 1 to 9, the impact resistance was evaluated for the ISO test piece obtained by the same method as the above-mentioned heat resistance evaluation. In detail, according to ISO-179-1 and ISO-179-2, the ISO test piece was cut to cut off the clamping parts at both ends of the ISO test piece, and a notch (cut) was applied to the central part of the ISO test piece to prepare a notched Charpy impact test piece. For the Charpy impact test piece thus obtained, as an evaluation of the impact resistance, the Charpy impact strength (unit: kJ / m 2 ).

[0181] [Evaluation of mechanical strength]

[0182] In each of Examples 1 to 18 and Comparative Examples 1 to 9, the mechanical strength was evaluated using ISO test pieces obtained by the same method as the above-mentioned heat resistance evaluation. Specifically, as one of the mechanical strength evaluations, the tensile strength (unit: MPa) of the ISO test pieces was measured by a measurement method based on ISO-527.

[0183] In addition, in the evaluation of mechanical strength, the parallel portion of the ISO test piece obtained as above was machined to produce a short strip-shaped test piece of length × width × thickness = 80 mm × 10 mm × 4 mm. The bending strength (unit: MPa) and bending modulus (unit: MPa) of the test piece were measured by the measurement method based on ISO-178 under an environment of temperature 23°C and humidity 50%.

[0184] [Evaluation results]

[0185] The content ratio (mass parts) of each component of the PPE-based resin composition of Examples 1 to 18 and Comparative Examples 1 to 9 and the results of the above-mentioned evaluations are shown in Tables 2-1 to 2-3. It should be noted that in Tables 2-1 to 2-3, the "total content of component (d)" refers to the total content (mass parts) of components (d-1) to (d-3) contained as phosphorus-based flame retardants (d) in the PPE-based resin composition. "Phosphorus content (P)" refers to the content of the phosphorus component contained in the PPE-based resin composition, calculated based on the added amount. "Mass ratio (E / P)" refers to the mass ratio of the polyolefin resin in the PPE-based resin composition relative to the phosphorus component. When the PPE-based resin composition contains a polyolefin resin (e), the mass ratio (E / P) is the mass ratio of the above-mentioned polyolefin resin (e) relative to the phosphorus component. When the PPE-based resin composition contains component (x-1) or component (x-2) as the polyolefin resin (x) instead of the polyolefin resin (e), the mass ratio (E / P) is the mass ratio of the polyolefin resin (x) to the phosphorus component. Similarly, when the PPE-based resin composition contains component (y-1) as the polyethylene wax (y) instead of the polyolefin resin (e), the mass ratio (E / P) is the mass ratio of the polyethylene wax (y) to the phosphorus component. "DTUL" refers to the deflection temperature under load.

[0186] In Examples 1 to 18, as shown in Tables 2-1 and 2-2, evaluation results of tracking resistance, impact resistance, flame retardancy, heat resistance, and mechanical strength (tensile strength, flexural strength, and flexural modulus) were obtained.

[0187] Specifically, as the evaluation results of the tracking resistance of each of Examples 1 to 18, the CTI values ​​shown in Tables 2-1 and 2-2 can be obtained. In Examples 1 to 18, the CTI values ​​are all 250V or more. Among them, in Examples 1, 2, 4 to 6, 9, 11 to 13, and 16 to 18, the CTI values ​​are 275V or more. In particular, in Example 11, even when the component (i-1) as the black pigment (i) is increased compared to other examples, a high CTI value (=275V) can be obtained.

[0188] In addition, as the evaluation results of the impact resistance of each of Examples 1 to 18, the Charpy impact strength shown in Tables 2-1 and 2-2 was obtained. In Examples 1 to 18, the Charpy impact strength was 9.0 kJ / m 2 Among them, in Examples 1, 2, 5 to 9, 11 to 14, and 18, the Charpy impact strength is 9.4 kJ / m 2 In particular, in Example 10, even though the styrene resin (b) which is effective for improving the impact resistance is not contained, by adjusting the content ratio of the component (a-1) as the polyphenylene ether resin (a) and the component (e-1) as the polyolefin resin (e), it is possible to obtain 9.0 kJ / m 2 Charpy impact strength above .

[0189] In addition, as the evaluation results of the flame retardancy of each of Examples 1 to 18, as shown in Tables 2-1 and 2-2, the level based on the UL94V test can be obtained. In Examples 1 to 18, the level all satisfies V-0. In particular, in Example 16, by increasing the phosphorus-based flame retardant (d) and containing a styrene-based resin (b), and adjusting the content ratio of the polyphenylene ether-based resin (a) and the polyolefin resin (e), it is possible to ensure V-0 as a flame retardancy level and obtain a high Charpy impact strength (=9.0 kJ / m 2 In Example 18, the phosphorus-based flame retardant (d) and the polyolefin resin (e) were added in such a manner that the mass ratio (E / P) of the polyolefin resin (e) to the phosphorus component was within the range of 0.2 to 2.65, thereby ensuring V-0 as the flame retardancy level and obtaining a high CTI value (=275V) and a high Charpy impact strength (=9.4kJ / m 2 ).

[0190] In summary, all of Examples 1 to 18 can have both high tracking resistance with a CTI value of ≥ 250V and a Charpy impact strength of ≥ 9.0 kJ / m 2 Excellent impact resistance and excellent flame retardancy of grade "V-0".

[0191] In addition, as the evaluation results of the heat resistance of each of Examples 1 to 18, the DTUL shown in Tables 2-1 and 2-2 can be obtained. In Examples 1 to 18, the DTUL is above 100°C, and excellent heat resistance can be obtained. In addition, as the evaluation results of the mechanical strength of each of Examples 1 to 18, the values ​​of tensile strength, bending strength and bending modulus shown in Tables 2-1 and 2-2 can be obtained. Specifically, in Examples 1 to 18, the tensile strength is above 89 MPa, the bending strength is above 143 MPa, and the bending modulus is above 4,235 MPa. In this way, Examples 1 to 18 can all obtain high mechanical strength.

[0192] On the other hand, as shown in Table 2-3, the PPE-based resin composition of Comparative Example 1 is a resin composition that does not contain a polyolefin resin (e) having a skeleton derived from ethylene but contains a polyolefin resin (x) (component (x-1)) having no skeleton derived from ethylene. In such Comparative Example 1, the effect of improving the impact resistance by the combination of the polyphenylene ether-based resin (a) and the skeleton derived from ethylene in the polyolefin resin (e) is not obtained, and therefore the Charpy impact strength is less than 9.0 kJ / m 2 , compared with Examples 1 to 18, the impact resistance is low.

[0193] In addition, in Comparative Example 1, the mass ratio (E / P) of the polyolefin resin (x) to the phosphorus component in the PPE-based resin composition is in the range of 0.2 to 2.65, but in terms of flame retardancy, the grades (V-0, V-1, V-2) based on the UL94V test are not satisfactory and are poor (NG). It can be considered that the reason for this result is that the polyolefin resin that is the target of the above mass ratio (E / P) is a polyolefin resin (x) that does not have a skeleton derived from ethylene. That is, even if the above mass ratio (E / P) satisfies 0.2 to 2.65, if the polyolefin resin that is the target of the above mass ratio (E / P) is not a polyolefin resin (e) that has a skeleton derived from ethylene, it is difficult to improve the flame retardancy.

[0194] In addition, as shown in Table 2-3, the mass ratio (E / P) of the polyolefin resin (e) contained in the PPE-based resin composition of Comparative Example 2 relative to the phosphorus component is 2.69, which is a resin composition that does not meet the range (0.2 to 2.65) of the mass ratio (E / P) in the present invention. In this Comparative Example 2, in terms of flame retardancy, the level based on the UL94V test is V-1, and V-0 cannot be met. According to this result, it can be seen that even if the content of the phosphorus-based flame retardant (d) meets the range (15 to 27 parts by mass) in the present invention, if the mass ratio (E / P) of the polyolefin resin (e) in the PPE-based resin composition relative to the phosphorus component is not in the range of 0.2 to 2.65, it is difficult to improve the flame retardancy.

[0195] In addition, as shown in Table 2-3, the PPE-based resin compositions of Comparative Examples 3 and 4 are resin compositions that do not satisfy the content range (3 to 20 parts by mass) of the tracking resistance improver (f) in the present invention. In such Comparative Examples 3 and 4, the CTI value is less than 250 V in terms of tracking resistance. In particular, in Comparative Example 3, since the tracking resistance improver (f) is not contained, the CTI value is lower than that of Comparative Example 4.

[0196] In addition, as shown in Table 2-3, the PPE-based resin composition of Comparative Example 5 does not satisfy the content range (0.5 to 3 parts by mass) of the phosphorus-based stabilizer (g) in the present invention, and specifically does not contain the phosphorus-based stabilizer (g). In such Comparative Example 5, the flame retardancy is V-1 based on the UL94V test, and does not meet V-0.

[0197] In addition, as shown in Table 2-3, the PPE resin composition of Comparative Example 6 is a resin composition that does not meet the content range (more than 80% by mass) of the polyphenylene ether resin (a) in the present invention, specifically, among 100% by mass of the polyphenylene ether-containing resin (A), it contains 80% by mass of polyphenylene ether resin (a) and 20% by mass of styrene resin (b). It should be noted that when the polyphenylene ether-containing resin (A) containing polyphenylene ether resin (a) and styrene resin (b) is set to 100 parts by mass, the content (% by mass) of the polyphenylene ether resin (a) is the same as the content (parts by mass) relative to 100 parts by mass of the polyphenylene ether-containing resin (A). The same is true for the content of styrene resin (b). In this Comparative Example 6, the content of the polyphenylene ether resin (a) with excellent flame retardancy is small, so the level based on the UL94V test is V-1, and as flame retardancy, V-0 cannot be met.

[0198] In addition, as shown in Table 2-3, the PPE-based resin composition of Comparative Example 7 is a resin composition that does not satisfy the content range (0.3 to 7 parts by mass) of the polyolefin resin (e) having a skeleton derived from ethylene and the range (0.2 to 2.65) of the mass ratio (E / P) in the present invention. In this Comparative Example 7, the mass ratio (E / P) of the polyolefin resin (e) to the phosphorus component in the PPE-based resin composition is less than 0.2, and therefore, the Charpy impact strength is less than 9.0 kJ / m 2 , the impact resistance is lower than that of Examples 1 to 18. Furthermore, in Comparative Example 7, the content of the polyolefin resin (e) effective for improving the tracking resistance is less than 0.3 parts by mass, so the CTI value is less than 250V in terms of the tracking resistance.

[0199] In addition, as shown in Table 2-3, the PPE-based resin composition of Comparative Example 8 is a resin composition that does not contain the polyolefin resin (e) used in Examples 1 to 18, but contains a polyolefin resin (x) (component (x-2)) having a skeleton derived from ethylene but having lower fluidity than the polyolefin resin (e). Specifically, the MFR of component (x-2) showing fluidity is 0.4 g / 10 minutes (see Table 1-2) under the measurement conditions of a temperature of 190°C and a load of 2.16, which is lower than the MFR of the polyolefin resin (e) of Examples 1 to 18 (see Table 1-1). In such Comparative Example 8, the fluidity of component (x-2) is low, and therefore, component (x-2) is difficult to disperse in the PPE-based resin composition. Therefore, even if component (x-2) is a polyolefin resin having a skeleton derived from ethylene, since the dispersion state of component (x-2) in the PPE-based resin composition is deteriorated, the flame retardancy of Comparative Example 8 does not meet any level based on the UL94V test and is poor.

[0200] In addition, as shown in Table 2-3, the PPE-based resin composition of Comparative Example 9 is a resin composition that does not contain the polyolefin resin (e) used in Examples 1 to 18 but contains polyethylene wax (y) (component (y-1)). In detail, component (y-1) has a skeleton derived from ethylene, but it is a wax, and therefore, the fluidity of component (y-1) is extremely high compared to the above-mentioned polyolefin resin (e). On this basis, the molecular weight of component (y-1) is smaller than that of the above-mentioned polyolefin resin (e). In this Comparative Example 9, the effect of improving various properties exhibited by the PPE-based resin composition of Examples 1 to 18, which contains a polyolefin resin (e) having moderate fluidity (for example, an MFR of 0.5 to 100 g / 10 minutes under the measurement conditions of a temperature of 190°C and a load of 2.16), cannot be obtained. That is, in terms of tracking resistance, the CTI value is less than 250V, and in terms of impact resistance, the Charpy impact strength is less than 9.0 kJ / m 2 In particular, in Comparative Example 9, component (y-1) in the PPE-based resin composition appeared on the surface layer due to poor dispersibility, and thus the flame retardancy was poor.

[0201] [Table 2-1]

[0202]

[0203] [Table 2-2]

[0204]

[0205] [Table 2-3]

[0206]

[0207] It should be noted that the present invention is not limited to the above-mentioned embodiments and examples, and the schemes formed by appropriately combining the above-mentioned constituent elements are also included in the present invention. In addition, other embodiments, examples and application technologies implemented by those skilled in the art based on the above-mentioned embodiments are all included in the scope of the present invention.

[0208] Industrial Applicability

[0209] The PPE-based resin composition of the present invention can have high tracking resistance as well as excellent flame retardancy and impact resistance, and therefore can be extremely suitably used in various molded products such as battery cell cases.

Claims

1. A polyphenylene ether resin composition, characterized in that It contains at least a polyphenylene ether resin (a), The present invention comprises 5 to 25 parts by mass of an inorganic filler (c), 15 to 27 parts by mass of a phosphorus-based flame retardant (d), 0.3 to 7 parts by mass of a polyolefin resin (e) having a skeleton derived from ethylene, 3 to 20 parts by mass of a tracking resistance improver (f), and 0.5 to 3 parts by mass of a phosphorus-based stabilizer (g), relative to 100 parts by mass of a polyphenylene ether-containing resin (A) containing more than 80% by mass of the polyphenylene ether-based resin (a). The mass ratio of the polyolefin resin (e) to the phosphorus component in the polyphenylene ether resin composition is 0.2 to 2.

65. The polyolefin resin (e) has a melt flow rate of 0.5 to 100 g / 10 min under measurement conditions of a temperature of 190° C. and a load of 2.16 kg as measured in accordance with JIS K7210.

2. The polyphenylene ether resin composition according to claim 1, characterized in that The polyphenylene ether-containing resin (A) contains 85 to 100% by mass of the polyphenylene ether-based resin (a) and 0 to 15% by mass of the styrene-based resin (b).

3. The polyphenylene ether resin composition according to claim 1 or 2, characterized in that The tracking resistance improver (f) includes at least one selected from the group consisting of alkaline earth metal salts, metal hydroxides, nitrogen-containing compounds, inorganic acid metal compounds, and layered double hydroxides.

4. The polyphenylene ether resin composition according to claim 1 or 2, characterized in that: The tracking resistance improver (f) is calcium carbonate.

5. The polyphenylene ether resin composition according to claim 1 or 2, characterized in that: The inorganic filler (c) includes at least one selected from the group consisting of glass fiber, mica and talc.

6. A molded product, characterized in that: The polyphenylene ether resin composition is formed from the polyphenylene ether resin composition according to claim 1 or 2.

7. The molded article according to claim 6, characterized in that It is the battery cell housing.

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