Resin composition and molded article

Abstract

To provide a resin composition that offers a well-balanced combination of heat resistance, impact resistance, and fluidity, and a molded article including the resin composition.SOLUTION: A resin composition contains (A) polyphenylene ether resin, (B) polyethylene, and (C) styrenic thermoplastic elastomer. Relative to the total of 100 pts.mass of the component (A), component (B), and component (C), the component (A) is 50-88 pts.mass, component (B) is 10-40 pts.mass, and component (C) is 2-20 pts.mass. The component (B) has a viscosity average molecular weight (Mv) of 300,000 or more and 2,000,000 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition and a molded article. [Background technology]

[0002] Many thermoplastic resins are used as resin molding materials in a wide variety of applications, including electronic and electrical parts, office automation equipment parts, audiovisual equipment parts, and automotive parts. In recent years, there has been a demand for improved fluidity during hot melt processing to increase communication speed and miniaturization / precision of resin parts for information and communication devices, etc., improved heat resistance to allow for the miniaturization and integration of parts, and improved impact resistance and rigidity to prevent breakage and cracking due to the increasingly complex shapes of parts. In this context, many resin compositions have been proposed in which polyethylene is added to polyphenylene ether, particularly from the viewpoint of impact resistance (see, for example, Patent Documents 1 to 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2-110147 [Patent Document 2] Special Publication No. 2007-500283 [Patent Document 3] Japanese Patent Application Laid-Open No. 2008-274039 Summary of the Invention [Problem to be solved by the invention]

[0004] However, compositions in which common polyethylenes such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE) are added to polyphenylene ether have the problem that, although they have excellent impact resistance, their heat resistance is extremely reduced. Therefore, there is a demand for resin compositions with improved heat resistance, impact resistance, and fluidity.

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition having an excellent balance of heat resistance, impact resistance, and fluidity, and a molded article containing the resin composition. [Means for solving the problem]

[0006] As a result of extensive research conducted by the present inventors in order to solve the above problems, they discovered that a resin composition having an excellent balance of heat resistance, impact resistance, and fluidity can be obtained by blending a polyphenylene ether resin, a specific polyethylene, and a styrene-based thermoplastic elastomer in specific proportions, and thus completed the present invention.

[0007] That is, the present invention is as follows. [1] (A) polyphenylene ether resin, (B) polyethylene, and (C) styrene-based thermoplastic elastomer, Including, the amount of the component (A) is 50 to 88 parts by mass, the amount of the component (B) is 10 to 40 parts by mass, and the amount of the component (C) is 2 to 20 parts by mass, relative to 100 parts by mass in total of the component (A), the component (B), and the component (C); A resin composition characterized in that the viscosity average molecular weight (Mv) of the component (B) is 300,000 or more and 2,000,000 or less. [2] The resin composition according to [1], wherein the viscosity average molecular weight (Mv) of the component (B) is 500,000 or more and 1,000,000 or less. [3] The resin composition according to [1] or [2], wherein the total mass of the component (A), the component (B), and the component (C) is 70 mass% or more relative to 100 mass% of the resin composition. [4] The resin composition according to any one of [1] to [3], wherein the reduced viscosity of the component (A) is 0.20 to 0.50 dL / g. [5] The resin composition according to any one of [1] to [4], wherein the weight average molecular weight of the component (C) is 50,000 or more and 100,000 or less. [6] The resin composition according to any one of [1] to [5], wherein the component (C) contains at least one aromatic vinyl polymer block (X) mainly composed of structural units derived from an aromatic vinyl compound containing styrene, and the content of the aromatic vinyl polymer block (X) in 100% by mass of the component (C) is 25 to 40% by mass. [7] A molded article comprising the resin composition according to any one of [1] to [6]. [Effects of the Invention]

[0008] According to the present invention, it is possible to obtain a resin composition having an excellent balance of heat resistance, impact resistance, and fluidity, and a molded article containing the resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content.

[0010] [Resin composition] The resin composition according to the present embodiment is a resin composition comprising (A) a polyphenylene ether resin, (B) polyethylene, and (C) a styrene-based thermoplastic elastomer, in which the amounts of the (A) component, the (B) component, and the (C) component are 50 to 88 parts by mass, 10 to 40 parts by mass, and 2 to 20 parts by mass, relative to 100 parts by mass of the total of the (A), (B), and (C) components, and the viscosity average molecular weight Mv of the (B) component is 300,000 or more and 2,000,000 or less.

[0011] [(A) Polyphenylene ether resin] The polyphenylene ether resin (A) of this embodiment can contain polyphenylene ether (sometimes referred to as "PPE" in this specification) and a polystyrene resin. The PPE resin may be a mixed resin made of PPE and a polystyrene resin, or may be a resin made of PPE alone. Since the PPE-based resin contains PPE, the resin composition of this embodiment has even more excellent heat resistance.

[0012] Examples of the PPE include a homopolymer having a repeating unit structure represented by the following formula (1) and a copolymer having a repeating unit structure represented by the following formula (1). The above PPE may be used alone or in combination of two or more. [ka] In the above formula (1), R 1 , R 2 , R 3 , and R 4 are each independently a monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, a secondary alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, and a halohydrocarbonoxy group in which at least two carbon atoms separate the halogen atom from the oxygen atom.

[0013] From the viewpoint of fluidity, toughness, and chemical resistance during processing, the PPE preferably has a reduced viscosity of 0.15 to 1.0 dL / g, more preferably 0.20 to 0.50 dL / g, and even more preferably 0.20 to 0.40 dL / g, as measured using a 0.5 g / dL chloroform solution at 30°C with an Ubbelohde viscometer.

[0014] Examples of the PPE include, but are not limited to, homopolymers such as poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), and poly(2,6-dichloro-1,4-phenylene ether); and copolymers such as copolymers of 2,6-dimethylphenol and other phenols (e.g., 2,3,6-trimethylphenol and 2-methyl-6-butylphenol). Among these, from the viewpoints of the balance between toughness and rigidity when formed into a resin composition and ease of raw material availability, poly(2,6-dimethyl-1,4-phenylene ether) and copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred, and poly(2,6-dimethyl-1,4-phenylene ether) is more preferred.

[0015] The PPE can be produced by known methods, including, but not limited to, the oxidative polymerization of 2,6-xylenol by Hay using a complex of cuprous salt and amine as a catalyst, as described in U.S. Pat. No. 3,306,874, and the methods described in U.S. Pat. Nos. 3,306,875, 3,257,357, 3,257,358, JP-B-52-17880, JP-A-50-51197, and JP-A-63-152628.

[0016] The PPE may be a modified PPE obtained by reacting the homopolymer and / or copolymer with a styrene monomer or a derivative thereof, and / or an α,β-unsaturated carboxylic acid or a derivative thereof, wherein the graft or addition amount of the styrene monomer or a derivative thereof and / or the α,β-unsaturated carboxylic acid or a derivative thereof is preferably 0.01 to 10% by mass relative to 100% by mass of the PPE. Examples of methods for producing the modified PPE include a method in which the PPE is reacted in the presence or absence of a radical generator in a molten state, solution state, or slurry state at a temperature of 80 to 350°C.

[0017] The PPE may be a mixture of the homopolymer and / or copolymer and the modified PPE in any ratio.

[0018] The polystyrene resin contained in component (A) is preferably polystyrene or rubber-reinforced polystyrene (high impact polystyrene, HIPS).

[0019] As the component (A), a polyphenylene ether resin in which the mass ratio of PPE to polystyrene resin (PPE / polystyrene resin) is 100 / 0 to 10 / 90 can be used. From the viewpoints of fluidity, heat resistance, impact resistance, and rigidity, the mass ratio (PPE / polystyrene resin) is more preferably 100 / 0 to 30 / 70, and even more preferably 100 / 0 to 50 / 50. The polystyrene resins may be used singly or in combination of two or more.

[0020] From the viewpoint of fluidity, toughness, and chemical resistance during processing, the reduced viscosity of component (A), measured using a 0.5 g / dL chloroform solution at 30°C with an Ubbelohde viscometer, is preferably 0.20 to 0.50 dL / g, more preferably 0.20 to 0.40 dL / g, and even more preferably 0.20 to 0.35 dL / g.

[0021] The content of the (A) polyphenylene ether resin is 50 to 88 parts by mass, preferably 55 to 80 parts by mass, and more preferably 60 to 70 parts by mass, per 100 parts by mass of the total of the (A), (B), and (C) components. When the content of the (A) component is 50 parts by mass or more, the heat resistance tends to be excellent. When the content of the (A) component is 88 parts by mass or less, the flowability and impact resistance tend to be excellent.

[0022] [(B) Polyethylene] The polyethylene (B) of this embodiment is not particularly limited as long as it has a viscosity average molecular weight (Mv) of 300,000 or more and 2,000,000 or less, and may be an ethylene homopolymer or a copolymer of ethylene and another comonomer.

[0023] The other comonomers are not particularly limited, but examples thereof include α-olefins and vinyl compounds.

[0024] The α-olefin is not particularly limited, but examples thereof include α-olefins having 3 to 20 carbon atoms, and specific examples thereof include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, and 1-tetradecene.

[0025] The vinyl compound is not particularly limited, but examples thereof include vinylcyclohexane, styrene, and derivatives thereof.

[0026] If necessary, non-conjugated polyenes such as 1,5-hexadiene and 1,7-octadiene may also be used as other comonomers.

[0027] The copolymer of ethylene and another comonomer may be a ternary random polymer. The other comonomer may be used alone or in combination of two or more kinds.

[0028] When the (B) polyethylene of the present embodiment contains units derived from a comonomer (hereinafter also referred to as "comonomer units"), the content of the comonomer units in the (B) polyethylene is preferably 0.01 mol % or more and 1 mol % or less, more preferably 0.01 mol % or more and 0.5 mol % or less, and even more preferably 0.01 mol % or more and 0.1 mol % or less.

[0029] The method for producing the polyethylene (B) of this embodiment is not particularly limited, and any conventionally known polymerization method can be used. The catalyst used in the polymerization is not particularly limited, and examples thereof include Ziegler-Natta catalysts and metallocene catalysts disclosed in Japanese Patent Nos. 5782558, 5829257, and 4868853, and JP-A-10-218933.

[0030] The viscosity average molecular weight (Mv) of the polyethylene (B) of this embodiment is 300,000 or more and 2,000,000 or less, preferably 500,000 or more and 1,500,000 or less, and more preferably 500,000 or more and 1,000,000 or less. When the viscosity average molecular weight (Mv) is 300,000 or more, the heat resistance of the resin composition tends to be enhanced, whereas when the viscosity average molecular weight (Mv) is 2,000,000 or less, the resin composition tends to have excellent impact resistance.

[0031] The viscosity-average molecular weight (Mv) of (B) polyethylene can be determined by the following method: First, 4.5 mg of (B) polyethylene is weighed into a dissolution tube, and the air inside the dissolution tube is degassed using a vacuum pump and replaced with nitrogen. Then, 20 mL of decahydronaphthalene (containing 1 g / L of 2,6-di-t-butyl-4-methylphenol; hereafter, also referred to as "decalin") is added, and the mixture is stirred at 150°C for 1.5 hours to dissolve the (B) polyethylene and obtain a decalin solution. The resulting decalin solution is placed in a thermostatic bath at 135°C and the drop time (ts) between the marked lines is measured using a Cannon-Fenske type viscometer. As a blank, (B) the fall time (tb) of decalin alone without polyethylene is measured. The intrinsic viscosity (η) is calculated according to the following formula (ii) using the reduced viscosity (ηsp / C) of the polyethylene (B) determined according to the following formula (i). Furthermore, the viscosity average molecular weight (Mv) is calculated using the intrinsic viscosity (η) according to the following formula (iii). (ηsp / C)=(t s / t b-1) / C (unit: dL / g) Equation (i) (η)=(ηsp / C) / (1+(0.27×C×(ηsp / C))(Unit: dL / g)...Equation (ii) (Mv)=((η) / 6.8×10 4 ) 1.4925 ...Equation (iii) Here, C is the concentration of the decalin solution at 135°C and is calculated by the following formula (iv). C = ((B) mass of polyethylene (mg) / 1000) / (amount of decalin solution (mL) × 1.107) × 100 (unit: g / dL) Equation (iv)

[0032] The content of polyethylene (B) is 10 to 40 parts by mass, preferably 15 to 35 parts by mass, and more preferably 20 to 35 parts by mass, per 100 parts by mass of the total of components (A), (B), and (C). When the content of component (B) is 10 parts by mass or more, impact resistance tends to be excellent. On the other hand, when the content of component (B) is 40 parts by mass or less, heat resistance tends to be excellent.

[0033] [(C) Styrene-based thermoplastic elastomer] The styrene-based thermoplastic elastomer (C) of this embodiment is an unhydrogenated block copolymer and / or a hydrogenated product of the block copolymer, which contains at least one aromatic vinyl polymer block (X) mainly composed of structural units derived from an aromatic vinyl compound and at least one conjugated diene polymer block (Y) mainly composed of structural units derived from a conjugated diene compound, and which contains 50 mass % or more of structural units derived from styrene among the structural units derived from the aromatic vinyl compound.

[0034] With regard to the aromatic vinyl polymer block (X), the phrase "mainly composed of structural units derived from an aromatic vinyl compound" means that 50% by mass or more of the block is composed of structural units derived from an aromatic vinyl compound, more preferably 70% by mass or more, even more preferably 80% by mass or more, and most preferably 90% by mass or more of the structural units derived from an aromatic vinyl compound. The aromatic vinyl compound used to form the aromatic vinyl polymer block (X) is not particularly limited, and examples thereof include styrene, α-methylstyrene, vinyltoluene, etc., and one or more compounds selected from these may be used. Among these, it is particularly preferable to use only styrene.

[0035] Similarly, the term "mainly composed of structural units derived from a conjugated diene compound" of the conjugated diene polymer block (Y) means that 50% by mass or more of the structural units are derived from a conjugated diene compound, more preferably 70% by mass or more, even more preferably 80% by mass or more, and most preferably 90% by mass or more of the structural units derived from a conjugated diene compound. The conjugated diene compound used to form the conjugated diene polymer block (Y) is not particularly limited, and examples thereof include butadiene, isoprene, piperylene, 1,3-pentadiene, etc., and one or more compounds selected from these can be used. Among these, butadiene, isoprene, and combinations thereof are preferred.

[0036] Furthermore, the aromatic vinyl polymer block (X) may be, for example, a copolymer block in which a small amount of structural units derived from a conjugated diene compound are randomly bonded to an aromatic vinyl polymer block. Similarly, the conjugated diene polymer block (Y) may be, for example, a copolymer block in which a small amount of structural units derived from an aromatic vinyl compound are randomly bonded to a conjugated diene polymer block.

[0037] The component (C) used in this embodiment preferably contains the aromatic vinyl polymer block (X) in an amount of 10 to 90 mass %, more preferably 20 to 60 mass %, and most preferably 25 to 40 mass %, based on 100 mass % of the component (C). Furthermore, the component (C) used in this embodiment preferably contains the conjugated diene polymer block (Y) in an amount of 10 to 90 mass%, more preferably 40 to 80 mass%, and most preferably 60 to 75 mass%, based on 100 mass% of the component (C).

[0038] The bonding mode of the conjugated diene polymer block (Y) is not particularly limited and can be selected arbitrarily. The vinyl bond content (the proportion of 1,2-bonds and 3,4-bonds incorporated in the conjugated diene compound, among 1,2-bonds, 3,4-bonds and 1,4-bonds) is preferably 5 to 60%, more preferably 10 to 50%, and even more preferably 30 to 40%. The vinyl bond content can be determined using an infrared spectrophotometer or a nuclear magnetic resonance (NMR) spectrometer.

[0039] Furthermore, the component (C) used in this embodiment may be a block copolymer in which at least a portion has been hydrogenated (hydrogenated block copolymer). Here, the hydrogenated block copolymer refers to a copolymer obtained by subjecting the above-mentioned non-hydrogenated block copolymer to a hydrogenation treatment, thereby reducing the aliphatic double bonds derived from the polymer portion of the conjugated diene compound that may be contained in the aromatic vinyl polymer block (X) and the polymer portion of the conjugated diene compound that may be contained in the conjugated diene polymer block (Y). The hydrogenation rate of the hydrogenated block copolymer is preferably 50% or more, more preferably 80% or more, and most preferably 98% or more, based on the total amount of aliphatic double bonds derived from the polymer portion of the conjugated diene compound. The hydrogenation rate can be determined using an infrared spectrophotometer or a nuclear magnetic resonance (NMR) spectrometer.

[0040] The component (C) used in this embodiment is preferably a block copolymer in which the aromatic vinyl polymer block (X) and the conjugated diene polymer block (Y) have a bonding structure selected from XY, XYX, and XYXY. Among these, block copolymers having different bonding structures may be used in combination. Among these, a bonding structure selected from XYX and XYXY is more preferred, and a bonding structure of XYX is even more preferred.

[0041] Specific examples of the component (C) used in the present embodiment include, but are not limited to, styrene-butadiene block copolymers, styrene-butadiene-styrene block copolymers, styrene-isoprene block copolymers, styrene-isoprene-styrene block copolymers, styrene-(ethylene-butylene) block copolymers, styrene-(ethylene-butylene)-styrene block copolymers, styrene-(ethylene-propylene) block copolymers, styrene-(ethylene-propylene)-styrene block copolymers, and styrene-(ethylene-ethylene-propylene)-styrene block copolymers.

[0042] In this embodiment, the weight-average molecular weight of component (C) is preferably 50,000 to 220,000. When the weight-average molecular weight is within this range, the compatibility between components (A) and (B) is improved, and a resin composition can be obtained that has an excellent balance of heat resistance, mechanical properties, and molding flowability, and in particular, significantly improved impact resistance. From the same viewpoint, the weight average molecular weight of the component (C) is more preferably 50,000 to 200,000, even more preferably 50,000 to 150,000, and most preferably 50,000 to 100,000. The weight average molecular weight of the component (C) can be determined by a conventionally known method using gel permeation chromatography (mobile phase: chloroform, standard substance: polystyrene).

[0043] The component (C) that can be used in this embodiment may be a mixture of two or more types each having a different bonding type, a different aromatic vinyl compound type, a different conjugated diene compound type, a different vinyl bond amount, a different aromatic vinyl compound component content, a different hydrogenation rate, etc., as long as it does not go against the spirit of this embodiment.

[0044] Furthermore, the component (C) that can be used in this embodiment may be a modified block copolymer. The modified block copolymer referred to here refers to a block copolymer in which a portion of the main chain and / or side chain of the block copolymer has been modified with at least one functional group selected from the group consisting of a carboxy group, an acid anhydride group, an amino group, a hydroxy group, and a glycidyl group. Examples of methods for producing the modified block copolymer include (1) a method of melt-kneading and reacting the block copolymer and the modifying compound in a temperature range from the softening point of the block copolymer to 250°C inclusive, in the presence or absence of a radical initiator; (2) a method of reacting the block copolymer and the modifying compound in a solution at a temperature not higher than the softening point of the block copolymer; and (3) a method of reacting the block copolymer and the modifying compound at a temperature not higher than the softening point of the block copolymer without melting them, in the presence or absence of a radical initiator. Although any of these methods may be used, method (1) is preferred, and among method (1), the method carried out in the presence of a radical initiator is most preferred.

[0045] The content of the (C) styrene-based thermoplastic elastomer is 2 to 20 parts by mass, preferably 5 to 15 parts by mass, and more preferably 10 to 15 parts by mass, per 100 parts by mass of the total of the (A), (B), and (C) components. When the content of the (C) component is 2 parts by mass or more, the dispersibility of the (B) component is improved, and the impact resistance tends to be excellent. When the content of the (C) component is 20 parts by mass or less, the heat resistance tends to be excellent.

[0046] In the resin composition of this embodiment, when the entire resin composition is taken as 100% by mass, the total content of the above-mentioned components (A), (B), and (C) is preferably 70% by mass or more, more preferably 75% by mass or more, and even more preferably 80% by mass or more. It can also be 85% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, or even 100% by mass.

[0047] The resin composition of this embodiment may contain a matrix phase containing component (A) and a dispersed phase dispersed in the matrix phase. The dispersed phase preferably has an average particle size of 1 to 50 μm, more preferably 1 to 20 μm, and even more preferably 1 to 10 μm. When the average particle size of the dispersed phase is 1 μm or more, the heat resistance tends to be excellent, and when the average particle size is 50 μm or less, the impact resistance tends to be excellent. The method for measuring the average particle size of the dispersed phase is not particularly limited, but the average particle size (D50) can be measured by a laser granulometer using a solution in which the resin composition is dissolved in chloroform.

[0048] [Other ingredients] In addition to the above-described components (A), (B), and (C), the resin composition of the present embodiment may contain other thermoplastic resins other than (A) polyphenylene ether-based resin and (B) polyethylene, (C) thermoplastic elastomers other than styrene-based thermoplastic elastomers, inorganic fillers, colorants, flame retardants, other additives, and the like (hereinafter collectively referred to as "other components"), within the scope that does not impair the effects of the present embodiment.

[0049] The total content of the other components is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, when the entire resin composition is 100% by mass.

[0050] Examples of other thermoplastic resins besides the (A) polyphenylene ether resin and (B) polyethylene include polyphenylene sulfide, polyethersulfone, polysulfone, polycarbonate, polyacetal, etc., as well as polyester-based resins such as liquid crystal polymers, aromatic polyesters, polyarylates, polyethylene terephthalate, and polybutylene terephthalate; polyolefin-based resins such as polyethylene, polypropylene, α-olefin copolymers, and polymethylpentene; polyamide-based resins such as nylon 6, nylon 66, and aromatic nylon; and acrylic resins such as polymethyl methacrylate. Thermoplastic elastomers are not included as examples of other thermoplastic resins. These thermoplastic resins can be used alone or in combination of two or more.

[0051] Examples of the thermoplastic elastomer other than the (C) styrene-based thermoplastic elastomer include urethane-based, polyester-based, polyamide-based, fluorine-based, vinyl chloride-based, polyolefin-based, polybutadiene-based, polyisoprene-based, polyethylene-based, etc. These thermoplastic elastomers can be used alone or in combination of two or more.

[0052] By adding an inorganic filler as the other component to the resin composition of the present embodiment, the heat resistance, mechanical properties, dimensional stability, and the like can be improved. Examples of the inorganic filler include fibrous, acicular, granular, spherical, hollow, or plate-shaped inorganic reinforcing materials such as glass fiber, potassium titanate fiber, barium titanate fiber, gypsum fiber, brass fiber, ceramic fiber, boron whisker fiber, mica, talc, silica, calcium carbonate, kaolin, calcined kaolin, wollastonite, xonotlite, apatite, glass beads, hollow glass beads, and glass flakes. These inorganic fillers can be used alone or in combination of two or more. Furthermore, the inorganic filler may be surface-treated by a known method using a surface treatment agent such as a silane coupling agent.

[0053] The colorant is not particularly limited, but for example, one or more colorants selected from known organic dyes, pigments, and inorganic pigments can be used. Examples of the organic dyes and pigments include azo-based dyes and pigments such as azo lake dyes and pigments, benzimidazolone dyes and pigments, diarylide dyes and pigments, and condensed azo dyes and pigments; phthalocyanine-based dyes and pigments such as phthalocyanine blue and phthalocyanine green; isoindolinone dyes and pigments, quinophthalone dyes and pigments, quinacridone dyes and pigments, perylene dyes and pigments, anthraquinone dyes and pigments, perinone dyes and pigments, and condensed polycyclic dyes and pigments such as dioxazine violet; azine-based dyes and pigments; and carbon black. Examples of the inorganic pigment include metal oxides such as titanium oxide, zinc oxide, and chromium oxide, and composite metal oxides such as titanium yellow, cobalt blue, and ultramarine.

[0054] Examples of the flame retardant include phosphate ester compounds, phosphinates, phosphazenes, hydrated metal compounds, and silicones, with phosphate ester compounds and phosphinates being preferred. Examples of the phosphate ester compounds include monophosphate esters such as triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, and trixylenyl phosphate; and condensed phosphate esters such as resorcinol bis(diphenyl phosphate), resorcinol bis(dixylenyl phosphate), biphenyl bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), and bisphenol A bis(dicresyl phosphate). Among these, it is preferable to use condensed phosphate esters because they generate less gas during processing and have excellent thermal stability. Examples of the phosphinates include calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate. The flame retardants can be used alone or in combination of two or more.

[0055] In addition to the above, the other components may include other additives such as organic or metallic heat stabilizers (antioxidants), ultraviolet absorbers, light stabilizers, anti-dripping agents, plasticizers, flow improvers, lubricants, crystal nucleating agents, release agents, anti-blocking agents, antistatic agents, and spreading agents. The resin composition of the present embodiment may also contain various laser direct structuring (LDS) additives such as copper-chromium composite oxide, copper-chromium-manganese composite oxide, and copper-manganese-iron composite oxide, and the resin composition of the present embodiment containing an LDS additive can be suitably used for MIDs (molded circuit components) and the like.

[0056] [Method for producing resin composition] The method for producing the resin composition of the present embodiment is not particularly limited, but the resin composition can be produced by melt-kneading the above-mentioned components (A), (B), and (C), and, if necessary, the above-mentioned other components.

[0057] The melt kneader used for melt kneading is not particularly limited, and examples thereof include single-screw extruders, multi-screw extruders including twin-screw extruders, rolls, kneaders, Brabender plastographs, Banbury mixers, and other heat melt kneaders. Among these, twin-screw extruders are preferably used from the viewpoint of kneading properties. Examples of such twin-screw extruders include the ZSK series manufactured by Werner & Pfleiderer, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by The Japan Steel Works, Ltd.

[0058] The configuration of the extruder is not particularly limited, but for example, it is preferable to have a first raw material supply port on the upstream side with respect to the flow direction of the raw materials, a first vacuum vent downstream from the first raw material supply port, a second raw material supply port downstream from the first vacuum vent (if necessary, a third and a fourth raw material supply port may be further provided downstream of the second raw material supply port), and a second vacuum vent downstream from the second raw material supply port. In particular, it is more preferable to have a kneading section provided upstream of the first vacuum vent, a kneading section provided between the first vacuum vent and the second raw material supply port, and a kneading section provided between the second to fourth raw material supply ports and the second vacuum vent.

[0059] One specific embodiment of a method for producing the resin composition of this embodiment using a twin-screw extruder includes, for example, supplying each component to the first raw material supply port of the twin-screw extruder, setting the heat-melting zone at or above the melting temperature of the thermoplastic resin, and melt-kneading the components at a screw rotation speed of 100 to 1200 rpm, preferably 200 to 500 rpm. The components may be supplied to the twin-screw extruder all at once through the first raw material supply port, as described above, or may be supplied separately through second, third, and fourth raw material supply ports.

[0060] Furthermore, to reduce the generation of crosslinked or charred resins due to thermal history in the presence of oxygen, it is preferable to maintain the oxygen concentration of each raw material in the process line of the feed route to the extruder at less than 1.0% by volume. The feed route is not particularly limited, but a specific example may include, in order from a stock tank, piping, a gravimetric feeder with a refill tank, piping, a feed hopper, and a twin-screw extruder. A method for maintaining such a low oxygen concentration is not particularly limited, but an effective method is to introduce an inert gas into each process line with increased airtightness. Typically, it is preferable to introduce nitrogen gas to maintain the oxygen concentration at less than 1.0% by volume.

[0061] [Molded products and their manufacturing methods, etc.] The resin composition of the present embodiment can be molded to produce a molded article by using a conventionally known molding method such as injection molding, extrusion molding, press molding, blow molding, calendar molding, and casting molding. That is, the molded article of the present embodiment contains the resin composition of the present embodiment.

[0062] The molding method is not particularly limited, and known methods can be used. For example, a molded article having a predetermined shape can be produced by melting a resin composition in the cylinder of an injection molding machine and injecting the melted resin composition into a mold having a predetermined shape. Alternatively, a fibrous molded article can be produced by melting the resin composition in an extruder with a controlled cylinder temperature and spinning it through a die nozzle. Furthermore, a film- or sheet-shaped molded product can be produced by melting the resin composition in an extruder with a controlled cylinder temperature and extruding it through a T-die.

[0063] Furthermore, a molded article produced by such a method may have a coating layer formed on its surface, such as a paint, metal, or other type of polymer. That is, a laminate may be formed comprising the molded article of the present embodiment and a coating layer formed on at least a portion of the surface of the molded article. The coating layer may be one layer, or two or more layers. The lamination method is not particularly limited, and a suitable method may be adopted depending on the intended use and the shape of the molded article. [Example]

[0064] Hereinafter, the present embodiment will be described with reference to specific examples and comparative examples, but the present embodiment is not limited to these. The raw materials and measurement methods used in the examples and comparative examples are shown below.

[0065] 〔raw materials〕 <(A) Polyphenylene ether resin> (A-1) PPE was used, which was adjusted to a concentration of 0.5 g / dL using a chloroform solvent and had a reduced viscosity of 0.40 dL / g measured at 30°C using an Ubbelohde viscometer. (A-2) PPE was used, which was adjusted to a concentration of 0.5 g / dL using a chloroform solvent and had a reduced viscosity of 0.33 dL / g measured at 30°C using an Ubbelohde viscometer.

[0066] <(B) Polyethylene> (B-1) Polyethylene with a viscosity average molecular weight (Mv) of 300,000 was used. (B-2) Polyethylene with a viscosity average molecular weight (Mv) of 500,000 was used. (B-3) Polyethylene with a viscosity average molecular weight (Mv) of 900,000 was used. (B-4) Polyethylene with a viscosity average molecular weight (Mv) of 2,000,000 was used. (B-5) Polyethylene with a viscosity average molecular weight (Mv) of 3,000,000 was used. (B-6) Polyethylene with a viscosity average molecular weight (Mv) of 180,000 was used.

[0067] <(C) Styrene-based thermoplastic elastomer> (C-1) A styrene-(ethylene-butylene)-styrene block copolymer (SEBS) with a styrene-based block of 30% by mass and a weight-average molecular weight of 80,000 was used. (C-2) A styrene-(ethylene-butylene)-styrene block copolymer (SEBS) with a styrene-based block of 42% by mass and a weight-average molecular weight of 80,000 was used. (C-3) A styrene-(ethylene-butylene)-styrene block copolymer (SEBS) with a styrene-based block of 20% by mass and a weight-average molecular weight of 100,000 was used. (C-4) A styrene-(ethylene-butylene)-styrene block copolymer (SEBS) was used, with a styrene-based block of 32% by mass and a weight-average molecular weight of 160,000.

[0068] [Method of measuring characteristics] (1) Melt Volume Flow Rate (MVR) The pellets of the obtained resin composition were subjected to MVR (cm) at 300°C under a load of 5 kg in accordance with ISO1133. 3 The larger the value, the better the fluidity was judged to be.

[0069] (2) Deflection temperature under load (DTUL) The resulting resin composition pellets were dried at 80°C for 2 hours and then fed into a small injection molding machine (product name: IS-100GN, manufactured by Toshiba Machine Co., Ltd.) set at a cylinder temperature of 280°C, and JIS K7139 ISO dumbbells for evaluation were produced at a mold temperature of 80°C. The ISO dumbbells were then cut to produce test pieces for measuring deflection temperature under load (DTUL). Using the test pieces for measuring deflection temperature under load, the deflection temperature under load (DTUL, ISO 75: 1.8 MPa load) (°C) was measured. The higher the value, the better the heat resistance was judged to be.

[0070] (3) Notched Charpy impact strength Using the JIS K7139 ISO dumbbell molded in (2) above, test pieces for measuring Charpy impact strength were prepared. Using the test pieces for measuring Charpy impact strength, the notched Charpy impact strength (kJ / m) was measured at a temperature of 23°C in accordance with ISO179. 2 The larger the value, the better the impact resistance was judged to be.

[0071] (4) Dielectric constant (Dk) and dielectric loss tangent (Df) The resulting resin composition pellets were dried at 80°C for 2 hours and then fed into an injection molding machine (model: EC75SXII, manufactured by Toshiba Machine Co., Ltd.) with a cylinder temperature set to 300°C. Plate test specimens measuring 55 x 55 x 0.9 mm were prepared at a mold temperature of 90°C. The test specimens were left to stand for at least 24 hours in an atmosphere of 23°C and 50% RH. The dielectric constant and dielectric loss tangent were then measured under the following conditions using a network analyzer (model: N5224B, manufactured by Keysight Technologies, Inc.). The dielectric constant and dielectric loss tangent were calculated from the average values ​​of three test specimens. Lower values ​​indicated superior dielectric properties. (Measurement conditions) Resonator: Split-post dielectric resonator (model: N1501AE19, Keysight Technologies) Frequency: 10GHz

[0072] [Examples 1 to 9 and Comparative Examples 1 to 3] A twin-screw extruder [ZSK-26MC, manufactured by Coperion (Germany)] was used as the resin composition manufacturing device. The raw materials were fed using a hopper from an upstream feed port at a position L=0 from the upstream, assuming the total length of the extruder cylinder to be 1.0. The temperature was set at 320°C from the upstream feed port to the position L=0.4, and 280°C downstream, with the screw rotation speed set at 300 rpm and the discharge rate set at 10 kg / h. In addition, openings were made in the center and in the cylinder block immediately before the die, and residual volatile matter and oligomers were removed by vacuum suction at a vacuum level (absolute pressure) of 60 Torr. According to the composition shown in Table 1 below, the raw materials were supplied and melt-kneaded. The strand extruded from the tip of the extruder die was cooled in a SUS strand bath filled with cooling water, and then cut with a strand cutter to obtain resin composition pellets. The resin composition pellets thus obtained were subjected to the above-mentioned evaluations, and the results are shown in Table 1 below.

[0073] [Table 1] [Industrial Applicability]

[0074] The resin composition of the present invention has an excellent balance of heat resistance, impact resistance, and fluidity, as well as excellent dielectric properties, and can therefore be suitably used as components for automobile parts, electrical and electronic equipment parts, industrial parts, household electrical appliances, etc. In particular, because of its excellent heat resistance and dielectric properties, it can be suitably used as components for high-frequency communication and electronic equipment, and specifically can be used for housings, antennas, connectors, switches, filters, converters, couplers, circulators, isolators, capacitors, inductors, coils, resonators, FPCs, etc.

Claims

1. (A) a polyphenylene ether resin, (B) polyethylene, and (C) a styrene-based thermoplastic elastomer, Including, the amount of the component (A) is 50 to 88 parts by mass, the amount of the component (B) is 10 to 40 parts by mass, and the amount of the component (C) is 2 to 20 parts by mass, relative to 100 parts by mass in total of the component (A), the component (B), and the component (C); A resin composition characterized in that the viscosity average molecular weight (Mv) of the component (B) is 300,000 or more and 2,000,000 or less.

2. 2. The resin composition according to claim 1, wherein the viscosity average molecular weight (Mv) of the component (B) is 500,000 or more and 1,000,000 or less.

3. The resin composition according to claim 1 or 2, wherein the total mass of the component (A), the component (B), and the component (C) is 70 mass% or more relative to 100 mass% of the resin composition.

4. The resin composition according to claim 1 or 2, wherein the reduced viscosity of the component (A) is 0.20 to 0.50 dL / g.

5. The resin composition according to claim 1 or 2, wherein the weight average molecular weight of the component (C) is 50,000 or more and 100,000 or less.

6. 3. The resin composition according to claim 1, wherein the component (C) comprises at least one aromatic vinyl polymer block (X) mainly composed of structural units derived from an aromatic vinyl compound containing styrene, and the content of the aromatic vinyl polymer block (X) in 100% by mass of the component (C) is 25 to 40% by mass.

7. A molded article comprising the resin composition according to claim 1.

Images