Antenna member

Abstract

An antenna member includes an injection molded body made of a thermoplastic resin composition, and a metal coating on at least a portion of the injection molded body. The thermoplastic resin composition includes a polyphenylene ether resin, and the deflection temperature under load of the thermoplastic resin composition is 120 °C or higher, and when a temperature range while the thermoplastic resin composition is heated from -30 °C to 120 °C is divided into temperature ranges with intervals of 10 °C, and a low temperature side and a high temperature side of respective two adjacent temperature ranges are defined as a low temperature range and a high temperature range, respectively, a low temperature range expansion coefficient of the resin composition in a TD direction (mm / mm / °C) and a high temperature range expansion coefficient of the resin composition in the TD direction (mm / mm / °C), as measured by the method described in ISO 11359, satisfy the following relationship in any of the two adjacent temperature ranges: -50 <= ((high temperature range expansion coefficient - low temperature range expansion coefficient) / low temperature range expansion coefficient) x 100 <= 50. Figure 1

Description

Antenna components

[0001] The present invention relates to an antenna member.

[0002] Conventionally, antenna components have been made of metals and ceramics due to their mechanical properties and heat resistance. However, there is a demand for lightweight antennas, particularly in base stations for communication equipment, in order to facilitate installation and ease of handling during assembly, and there is a demand for resins.

[0003] For example, filters are made of metal or ceramic, and many surfaces must be coated with metal to filter radio waves. When replacing them with resin, a resin that can be coated by plating or sputtering is required. Furthermore, antenna elements (pendulums) in communications equipment can function as antennas by wiring metal circuits on resin with a low dielectric loss tangent.

[0004] Meanwhile, surface-mounted dielectric antennas for use in mobile communication devices such as mobile phones and wireless LANs have been proposed, which are made of dielectric ceramics alone, resins alone, and ceramic-containing resin compositions. For example, a surface-mounted dielectric antenna having an antenna base made of ceramics alone or resin alone (see Patent Document 1), a foam made of a styrene-based resin with a syndiotactic structure and a dielectric constant real part of approximately 18 that has good plating properties, and a method for producing the same (see Patent Document 2), have been disclosed. Furthermore, a resin composition in which spherical dielectric ceramic powder is mixed with a resin material at a ratio of 40 vol% to 70 vol% (volume %) in the composition (see Patent Document 3), and a composite material in which metal titanate fibers with an aspect ratio adjusted to 3 to 5 to enable high loading and a thermoplastic resin or the like are combined with the same (see Patent Document 4) have been disclosed.

[0005] JP-A-9-98015 JP-A-10-45936 Patent No. 3930814 Patent No. 2992667

[0006] When a resin composition is used for such an antenna member, it is required to have excellent mechanical properties, electrical properties, and heat resistance, as well as excellent dimensional stability. Furthermore, from the viewpoint of easily molding into a desired shape, molding by injection molding is required. Furthermore, a material that can be metal-coated by plating or sputtering and the metal coating does not peel off at high temperatures is required. Specifically, since both components generate heat during communication, the resin itself must be heat-resistant, and it must exhibit little dimensional change even at high temperatures and not peel off the metal coating. Antennas are exposed to the external environment and, since they contain heat-generating components inside, their internal temperatures can become very high. Since antenna properties must be maintained even at high temperatures, materials with low dielectric constants and dielectric loss tangents are required. Furthermore, resins capable of forming circuits are also required. From the viewpoint of forming circuits, materials that can exhibit antenna properties at high frequencies of 1 GHz or higher and maintain low dielectric loss tangents even at high temperatures are required.

[0007] Furthermore, with the recent spread of 5G communications, there is a demand for communication base stations capable of 5G communications. As communication speeds increase, base stations generate more heat, which requires heavy heat sinks for heat dissipation, resulting in a significant increase in overall weight, driving demand for weight reduction. Antenna filters, in particular, are made of metal or ceramic and account for a significant portion of the base station's weight. While resin-based antenna filters can reduce weight and simplify the installation process, they require a metal coating, posing challenges in maintaining resin-to-metal adhesion. Furthermore, since antenna pendulums require metal circuits, not only is resin-to-metal adhesion required, but materials with low dielectric loss tangents are also required to maximize antenna performance. As communications become more advanced, there is a demand for materials that can handle information at all frequencies, from low to high. Furthermore, with the recent expansion of communications coverage, antenna components are increasingly required to maintain the various characteristics described above while also demonstrating these properties in low, high, and humid environments.

[0008] Therefore, the present invention aims to provide an antenna member that is molded by injection molding, has little change in dimension or dielectric tangent at high temperatures while maintaining adhesion to a metal coating, and is adaptable to any environment, including low temperatures, high temperatures, and humidity.

[0009] As a result of intensive research into solving the above-mentioned problems, the inventors discovered that using a specific resin composition for an antenna component can contribute to reducing the weight of communication devices and simplifying the assembly process while maintaining antenna performance in any environment, and thus arrived at the present invention.

[0010] That is, the present invention is as follows: [1] An antenna member having an injection-molded article made of a thermoplastic resin composition, the antenna member being used by metal-coating at least a portion of the injection-molded article, the thermoplastic resin composition comprising (A-a) a polyphenylene ether-based resin, the thermoplastic resin composition having a deflection temperature under load (DTUL) of 120°C or higher, and the temperature of the thermoplastic resin composition when raised from -30°C to 120°C is divided into temperature ranges of 10°C intervals, with the lower temperature side of two adjacent temperature ranges being the lower temperature range and the higher temperature side being the higher temperature range, the low temperature expansion coefficient (mm / mm / °C) in the TD direction of the resin composition measured by the method described in ISO 11359 in the lower temperature range and the high temperature expansion coefficient (mm / mm / °C) in the TD direction of the resin composition measured by the method described in ISO 11359 in the higher temperature range satisfying the following relationship in both of the two adjacent temperature ranges: -50≦((High temperature expansion coefficient−Low temperature expansion coefficient) / Low temperature expansion coefficient)×100≦50 [2] The antenna member according to [1], wherein the temperature dependence of the dielectric dissipation factor at 28 GHz of the thermoplastic resin composition satisfies the following conditions: 1. When the DTUL is 120°C or higher and lower than 140°C, the difference between the dielectric dissipation factor at 23°C and the dielectric dissipation factor at 120°C is 0.004 or less. 2. When the DTUL is 140°C or higher, the difference between the dielectric dissipation factor at 23°C and the dielectric dissipation factor at 140°C is 0.004 or less. [3] The temperature of the thermoplastic resin composition is increased from -30°C to 120°C, and the average coefficient of expansion in the TD direction of the resin composition is 10×10 －５ [4] The antenna member according to [1] or [2], wherein the temperature of the thermoplastic resin composition is increased from -30°C to 120°C, and the temperature is divided into temperature ranges of 10°C each, and the maximum coefficient of expansion of the resin composition in the TD direction is measured by the method described in ISO 11359 for each temperature range, and the maximum coefficient of expansion of the resin composition in the TD direction is 10 x 10 －５The antenna member according to [3], wherein the thermoplastic resin composition contains (A-b) a crystalline resin. [6] The antenna member according to any one of [1] to [5], wherein the thermoplastic resin composition contains (B) an inorganic filler at 10% by mass or more. [7] The antenna member according to any one of [1] to [6], wherein the thermoplastic resin composition contains (A-a) a polyphenylene ether resin at 10% by mass or more. [8] The antenna member according to any one of [1] to [7], wherein the thermoplastic resin composition is used in an outdoor or indoor antenna base station. [9] The antenna member according to any one of [1] to [8], wherein the metal coating is formed by chromic acid etching electroless copper plating.

[10] The antenna member according to any one of [1] to [9], wherein the metal layer does not crack after being left for 2000 hours at 85°C and 85% humidity after forming a metal coating by chromic acid etching electroless copper plating.

[11] The antenna member according to any one of [1] to

[10] , wherein the thermoplastic resin composition contains (A-c-a) a polystyrene-based resin.

[12] The antenna member according to any one of [1] to

[11] , wherein the thermoplastic resin composition contains (A-c-b) a block copolymer containing at least one block mainly composed of aromatic vinyl monomer units and at least one block mainly composed of conjugated diene monomer units, and / or a hydrogenated product of the block copolymer.

[13] The antenna member according to any one of [1] to

[12] , wherein the antenna member is an antenna filter.

[14] The antenna member according to any one of [1] to

[12] , wherein the antenna member is an antenna element.

[0011] According to the present invention, an antenna member can be obtained that is molded by injection molding, has small changes in dimensions and dielectric tangent at high temperatures while maintaining adhesion to a metal coating, and is applicable to all environments, including low temperatures, high temperatures, and humidity.

[0012] FIG. 2 is a diagram illustrating a method for cutting out a test piece from an evaluation ISO dumbbell to measure the expansion coefficient in the examples.

[0013] The present invention will be described in detail below.

[0014] The antenna member of this embodiment has an injection-molded article made of a thermoplastic resin composition, and is used by metallizing at least a portion of the injection-molded article, the thermoplastic resin composition comprising (A-a) a polyphenylene ether-based resin, the thermoplastic resin composition having a deflection temperature under load (DTUL) of 120°C or higher, and the temperature of the thermoplastic resin composition when raised from -30°C to 120°C is divided into temperature ranges of 10°C intervals, with the lower temperature side of two adjacent temperature ranges being the low temperature range and the higher temperature side being the high temperature range, the low temperature expansion coefficient (mm / mm / °C) in the TD of the resin composition measured by the method described in ISO 11359 in the low temperature range and the high temperature expansion coefficient (mm / mm / °C) in the TD of the resin composition measured by the method described in ISO 11359 in the high temperature range satisfy the following relationship in both of the two adjacent temperature ranges: −50≦((high temperature expansion coefficient−low temperature expansion coefficient) / low temperature expansion coefficient)×100≦50

[0015] Each component of the thermoplastic resin composition of the present embodiment will be described in detail below.

[0016] [(A) Thermoplastic Resin] In this embodiment, the (A) thermoplastic resin refers to a resin component excluding fillers, inorganic fillers, etc. Examples of such a resin component include various resins used for molding, such as polyphenylene ether resins, polyester resins, polyamide resins, polycarbonate resins, vinyl resins, olefin resins, acrylic resins, and aromatic resins.

[0017] The thermoplastic resin (A) of this embodiment contains the polyphenylene ether resin (Aa), which can improve the adhesion to the metal coating and the temperature dependency of the dielectric loss tangent.

[0018] The thermoplastic resin (A) of this embodiment may also contain a resin component, such as an olefin-based thermoplastic elastomer or a hydrogenated block copolymer, that is primarily used to improve impact resistance.

[0019] Furthermore, the thermoplastic resin (A) of the present embodiment may simultaneously contain the crystalline resin (A-b) and other thermoplastic resins, such as polyester-based resins, polyamide-based resins, polycarbonate-based resins, vinyl-based resins, olefin-based resins, acrylic-based resins, and aromatic-based resins.

[0020] Olefin resins are preferably used from the viewpoint of low dielectric loss tangent, and resins having sufficient heat resistance are more preferred, and examples thereof include polyester resins such as polyethylene naphthalate (PEN), polyethylene terephthalate (PET), and polybutylene terephthalate (PBT); and polyolefin polymers such as cyclic olefin polymers (COP), cycloolefin copolymers, and methylpentene polymers (TPX).

[0021] Examples of the olefin-based thermoplastic elastomer include polyolefin homopolymers such as polyethylene and polypropylene, and polyolefin copolymers such as ethylene-propylene copolymer, ethylene-butylene copolymer, and ethylene-octene copolymer. In particular, examples of polyethylene homopolymers include high-pressure low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE).

[0022] Examples of the hydrogenated block copolymer include a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of a polystyrene block and a conjugated diene compound polymer block.

[0023] The structure of the block copolymer before hydrogenation is not particularly limited. For example, when the polystyrene block chain is represented by S and the conjugated diene compound polymer block chain is represented by B, the block copolymer may have the structure S-B-S, SB-S-B, (S-B-) ４ -S, SBSBS, and the like structures are exemplified.

[0024] [(A-a) Polyphenylene Ether Resin] Specific examples of the (A-a) polyphenylene ether resin (hereinafter, may be simply referred to as "component (A-a)") in this embodiment include 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), poly(2,6-dichloro-1,4-phenylene ether), and the like, as well as polyphenylene ether copolymers such as copolymers of 2,6-dimethylphenol with other phenols (for example, copolymers with 2,3,6-trimethylphenol and copolymers with 2-methyl-6-butylphenol as described in JP-B No. 52-17880).

[0025] Among these, particularly preferred polyphenylene ethers are poly(2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or a mixture thereof.

[0026] Examples of the component (A-a) 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 component (A-a) may be used alone or in combination of two or more. 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 hydrocarbyloxy group, and a halohydrocarbyloxy group in which at least two carbon atoms separate the halogen atom from the oxygen atom.

[0027] The method for producing the polyphenylene ether resin (A-a) is not particularly limited as long as it is obtained by a known method. Examples thereof include the method described in U.S. Pat. No. 3,306,874, in which the resin is produced by oxidatively polymerizing, for example, 2,6-xylenol using a complex of a cuprous salt and an amine as a catalyst, and the production methods described in U.S. Pat. Nos. 3,306,875, 3,257,357, and 3,257,358, JP-A Nos. 50-51197, JP-B Nos. 52-17880, and 63-152628, etc.

[0028] The reduced viscosity of the polyphenylene ether resin (Aa) in this embodiment (measured using a 0.5 g / dL chloroform solution at 30°C using an Ubbelohde viscometer) is preferably in the range of 0.30 to 0.80 dL / g, more preferably 0.35 to 0.75 dL / g, and most preferably 0.38 to 0.55 dL / g. When the polyphenylene ether resin (Aa) has a reduced viscosity in this range, it is preferable because it has excellent properties such as impact resistance and heat resistance.

[0029] In the polyphenylene ether resin (Aa) of this embodiment, a blend of two or more polyphenylene ethers having different reduced viscosities can also be preferably used.

[0030] Various known stabilizers can also be suitably used to stabilize the polyphenylene ether resin (A-a). Examples of stabilizers include metal stabilizers such as zinc oxide and zinc sulfide, and organic stabilizers such as hindered phenol stabilizers, phosphorus stabilizers, and hindered amine stabilizers. The preferred amount of these stabilizers is less than 5 parts by mass per 100 parts by mass of the polyphenylene ether resin (A-a).

[0031] Furthermore, known additives that can be added to the polyphenylene ether resin (Aa) may be added in an amount of less than 10 parts by mass per 100 parts by mass of the polyphenylene ether resin (Aa).

[0032] The component (A-a) may be a modified polyphenylene ether obtained by reacting the homopolymer and / or the copolymer with a styrene-based 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-based 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 component (A-a).

[0033] Examples of methods for producing the modified polyphenylene ether include a method in which the modified polyphenylene ether 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.

[0034] As the polyphenylene ether, a mixture of the above homopolymer and / or copolymer and the above modified PPE in any ratio may be used.

[0035] In the case where the crystalline resin (A-b) described below is not contained, the content of the polyphenylene ether resin (A-a) relative to 100% by mass of the thermoplastic resin (A) is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more, from the viewpoint of being able to control the dielectric constant while maintaining heat resistance and a low dielectric loss tangent. Furthermore, from the viewpoint of moldability, it is preferably 85% by mass or less.

[0036] Furthermore, in the case where the crystalline resin (A-b) described below is contained, from the viewpoint of being able to control the dielectric constant while maintaining heat resistance and a low dielectric loss tangent, the content of the polyphenylene ether resin (A-a) relative to 100% by mass of the thermoplastic resin (A) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. From the viewpoint of flowability, it is preferably 90% by mass or less.

[0037] In particular, from the viewpoint of maintaining a low dielectric loss tangent in the high temperature region, when the total amount of the polyphenylene ether resin (A-a) and the crystalline resin (A-b) is taken as 100 parts by mass, the amount of the polyphenylene ether resin (A-a) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more. Furthermore, from the viewpoint of flowability, it is preferably 90 parts by mass or less.

[0038] [(A-b) Crystalline Resin] This embodiment may contain (A-b) crystalline resin. (A-ba) polyamide, (A-bb-b) polypropylene, and (A-bc) polyphenylene sulfide resin are suitable. Other crystalline resins that can be used include polyethylene, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyether ether ketone, liquid crystal polymer, and polytetrafluoroethylene.

[0039] A specific preferred content of each of the crystalline resins (A-b) is 90% by mass or less, more preferably 80% by mass or less, and even more preferably 85% by mass or less, when the entire thermoplastic resin composition is taken as 100% by mass.

[0040] In particular, from the viewpoint of maintaining a low dielectric loss tangent in a high temperature region, when the total amount of the polyphenylene ether resin (A-a) and the crystalline resin (A-b) is taken as 100% by mass, the amount of the crystalline resin (A-b) is 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0041] [(A-ba) Polyamide] The (A-ba) polyamide of the present embodiment (hereinafter, may be simply referred to as "(A-ba) component") is not particularly limited as long as it has an amide bond {-NH-C(=O)-} in the repeating unit of the polymer main chain.

[0042] Generally, polyamides are obtained by ring-opening polymerization of lactams, polycondensation of diamines and dicarboxylic acids, polycondensation of ω-aminocarboxylic acids, etc., but are not limited to resins obtained by these methods.

[0043] Specific examples of lactams include ε-caprolactam, enantholactam, ω-laurolactam, and the like.

[0044] The diamines are broadly classified into aliphatic, alicyclic, and aromatic diamines. Specific examples of the diamines include tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, and 1,8-octanediamine. Examples of the alkyl amine include aliphatic diamines such as 1,10-decanediamine, 1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, and 5-methyl-1,9-nonanediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine.

[0045] Dicarboxylic acids are broadly classified into aliphatic, alicyclic, and aromatic dicarboxylic acids, and specific examples of dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,1,3-tridecanedioic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and dimer acid.

[0046] Specific examples of aminocarboxylic acids include ε-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminonananoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-aminotridecanoic acid.

[0047] In this embodiment, any of these lactams, diamines, dicarboxylic acids and ω-aminocarboxylic acids can be used, either alone or as a mixture of two or more of them, and copolymerized polyamides obtained by polycondensation can be used.

[0048] Furthermore, it is also possible to suitably use those obtained by polymerizing these lactams, diamines, dicarboxylic acids and ω-aminocarboxylic acids in a polymerization reactor to the stage of low molecular weight oligomers and then increasing the molecular weight in an extruder or the like.

[0049] Particularly, examples of the (A-b-a) polyamides that can be suitably used in the present embodiment include polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6,12, polyamide 6 / 6,6, polyamide 6 / 6,12, polyamide MXD (m-xylylenediamine),6, polyamide 6,T, polyamide 9,T, polyamide 6,I, polyamide 6 / 6,T, polyamide 6 / 6,I, polyamide 6,6 / 6,T, polyamide 6,6 / 6,I, polyamide 6 / 6,T / 6,I, polyamide 6,6 / 6,T / 6,I, polyamide 6 / 12 / 6,T, polyamide 6,6 / 12 / 6,T, polyamide 6 / 12 / 6,I, and polyamide 6,6 / 12 / 6,I.

[0050] Among these, polyamides obtained by copolymerizing a plurality of polyamides using an extruder, etc. Among these, preferred polyamides are one or more selected from aliphatic polyamides such as polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, and polyamide 12; and semi-aromatic polyamides such as polyamide 9,T, polyamide 6 / 6,T, polyamide 6,6 / 6,T, polyamide 6,6 / 6,I, and polyamide MXD,6, and more preferred are one or more selected from polyamide 6,6, polyamide 6, polyamide 9,T, and polyamide 6,6 / 6,I.

[0051] The polyamide (A-ba) according to this embodiment preferably has dicarboxylic acid units (a) containing 60 to 100 mol % of terephthalic acid units and diamine units (b) containing 60 to 100 mol % of aliphatic diamine units having 9 to 12 carbon atoms, from the viewpoint of water absorbency and heat resistance.

[0052] [[Dicarboxylic acid unit (a)]] In this embodiment, the dicarboxylic acid unit (a) contains 60 to 100 mol %, preferably 70 to 100 mol %, more preferably 80 to 100 mol %, even more preferably 90 to 100 mol %, and even more preferably 100 mol % of terephthalic acid units. When the molar ratio is within this range, the resin composition has excellent heat resistance. Furthermore, the resin composition tends to have excellent high-cycle moldability when molding complex-shaped or large molded articles.

[0053] The dicarboxylic acid unit (a) may contain a dicarboxylic acid unit other than a terephthalic acid unit. Examples of such dicarboxylic acid units include, but are not limited to, units derived from aliphatic dicarboxylic acids such as malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, and suberic acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, and 4,4'-biphenyldicarboxylic acid. These units may be of one type alone or in combination of two or more types.

[0054] The dicarboxylic acid units other than the terephthalic acid units may be contained in the dicarboxylic acid units (a) in an amount of 40 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, still more preferably 10 mol% or less, and most preferably 0 mol%.

[0055] [[Diamine Unit (b)]] In this embodiment, the diamine unit (b) contains 60 to 100 mol %, preferably 70 to 100 mol %, more preferably 80 to 100 mol %, even more preferably 90 to 100 mol %, and still more preferably 100 mol % of aliphatic diamine units having a carbon number of 9 to 12. When the carbon number and the molar ratio of the diamine units are within the above ranges, a resin composition having an excellent balance between low water absorbency and heat resistance is obtained.

[0056] The diamine unit (b) may be linear or branched.

[0057] Examples of the linear aliphatic diamine constituting the diamine unit (b) include, but are not limited to, 1,9-nonanediamine (also called nonamethylenediamine), decamethylenediamine, undecamethylenediamine, and dodecamethylenediamine.

[0058] Examples of aliphatic diamines constituting the aliphatic diamine unit having a substituent branched from the main chain that constitutes the diamine unit (b) include, but are not limited to, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine (also referred to as 2-methyloctamethylenediamine), and 2,4-dimethyloctamethylenediamine.

[0059] The diamine unit (b) preferably contains a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit from the viewpoint of a balance between mechanical strength, low water absorbency, and heat resistance. In particular, it is preferable to use a 1,9-nonanediamine unit and a 2-methyl-1,8-octanediamine unit in combination.

[0060] When the diamine unit (b) contains 1,9-nonanediamine units and / or 2-methyl-1,8-octanediamine units, the molar ratio of the 1,9-nonanediamine units to the 2-methyl-1,8-octanediamine units (1,9-nonanediamine units / 2-methyl-1,8-octanediamine units) is preferably in the range of 100 / 0 to 20 / 80. This molar ratio is more preferably 95 / 5 to 60 / 40, and even more preferably 90 / 10 to 75 / 25. When this molar ratio is in this range, the resin composition tends to have particularly excellent heat resistance.

[0061] The diamine unit (b) may contain a diamine unit other than an aliphatic diamine unit having 9 to 12 carbon atoms. Examples of such diamine units include, but are not limited to, aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and 2-methylpentamethylenediamine (also referred to as 2-methyl-1,5-diaminopentane); alicyclic diamines such as 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclopentanediamine; and units derived from aromatic diamines such as metaxylylenediamine. These units may be used alone or in combination of two or more. The diamine units other than the aliphatic diamine units having 9 to 12 carbon atoms may be contained in the dicarboxylic acid units (ba) in an amount of 40 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, still more preferably 10 mol% or less, and most preferably 0 mol%.

[0062] Preferred examples of the (Aba) polyamide of this embodiment include polyamide 9,T, 10,T, and the like.

[0063] Furthermore, the polyamide (A-b-a) of this embodiment may contain, to the extent that the object of this embodiment is not impaired, lactam units such as butyrolactam, pivalolactam, ε-caprolactam, caprylolactam, enantholactam, and undecanolactam; aminocarboxylic acid units such as 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid; trivalent or higher polyvalent amine units such as bishexamethylenetriamine; and trivalent or higher polyvalent carboxylic acid units such as trimellitic acid, trimesic acid, and pyromellitic acid. These units may be used alone or in combination of two or more. The total proportion (mol %) of these units in the polyamide (A-b-a) is preferably 20 mol % or less, more preferably 10 mol % or less, and even more preferably 5 mol % or less, based on the entire polyamide.

[0064] [Content of (A-ba) Polyamide] In the thermoplastic resin composition of this embodiment, when the thermoplastic resin (A) is taken as 100% by mass, the content of component (A-ba) is preferably 25 to 75% by mass, more preferably 30 to 75% by mass, and even more preferably 30 to 70% by mass. When the content of component (A-ba) is within this range, a resin excellent in mechanical strength, low water absorbency, dimensional accuracy, and weld strength can be obtained.

[0065] Furthermore, in the thermoplastic resin composition of this embodiment, when the total of component (A-a) and component (A-ba) is taken as 100 parts by mass, the content of component (A-ba) is 50 to 95 parts by mass, preferably 60 to 95 parts by mass, and more preferably 60 to 90 parts by mass. When the content of component (A-ba) is within this range, the thermoplastic resin composition has excellent mechanical strength, low water absorbency, dimensional accuracy, and weld strength, and also enables high-cycle molding.

[0066] [(A-b-a) Method for Producing Polyamide] The method for producing polyamide (A-b-a) is not particularly limited, and examples thereof include the following various methods: 1) a method in which an aqueous solution or suspension of dicarboxylic acid and diamine, or an aqueous solution or suspension of a mixture of dicarboxylic acid and diamine salt with other components such as lactam and / or aminocarboxylic acid (hereinafter, these may be abbreviated as "the mixture") is heated and polymerized while maintaining the molten state (hereinafter, also referred to as "thermal melt polymerization method"); 2) a method in which an aqueous solution or suspension of dicarboxylic acid and diamine or a mixture thereof is heated and a precipitated prepolymer is removed ("prepolymer method"); 3) a method in which the degree of polymerization of polyamide obtained by thermal melt polymerization is increased while maintaining the solid state at a temperature below the melting point ("thermal melt polymerization / solid-state polymerization method"); 4) a method in which an aqueous solution or suspension of dicarboxylic acid and diamine or a mixture thereof is heated and the precipitated prepolymer is further melted again in an extruder such as a kneader and the degree of polymerization is increased ("prepolymer / extrusion polymerization method"); 5) A method of heating an aqueous solution or suspension of dicarboxylic acid and diamine or a mixture thereof, and maintaining the precipitated prepolymer in a solid state at a temperature below the melting point of the polyamide to increase its degree of polymerization ("prepolymer solid-state polymerization method"); 6) A method of polymerizing dicarboxylic acid and diamine or a mixture thereof while maintaining it in a solid state ("monomer solid-state polymerization method"); 7) A method of polymerizing "a salt of dicarboxylic acid and diamine" or a mixture thereof while maintaining it in a solid state ("salt solid-state polymerization method"); 8) A method of polymerization using a dicarboxylic acid halide and diamine equivalent to the dicarboxylic acid ("solution method").

[0067] The polymerization form in the method for producing polyamide (Aba) is not limited to the following, and examples thereof include a batch system and a continuous system.

[0068] The polymerization apparatus is not particularly limited, and known apparatuses (for example, autoclave-type reactors, tumbler-type reactors, extruder-type reactors such as kneaders, etc.) can also be used.

[0069] [Physical Properties of Polyamide (A-ba)] The terminal groups of the polyamide (A-ba) contained in the thermoplastic resin composition of this embodiment are involved in the reaction with the polyphenylene ether resin (A-a). Polyamide resins typically have amino groups or carboxyl groups as terminal groups. In general, as the concentration of terminal carboxyl groups increases, impact resistance tends to decrease and fluidity tends to improve. In addition, as the concentration of terminal amino groups increases, impact resistance tends to improve and fluidity tends to decrease. However, the physical properties of the thermoplastic resin composition of this embodiment are not limited to these trends.

[0070] The terminal amino group concentration of component (A-ba) is preferably 1 to 80 μmol / g, more preferably 5 to 60 μmol / g, even more preferably 10 to less than 45 μmol / g, and even more preferably 20 to 40 μmol / g. By keeping the terminal amino group concentration within this range, the thermoplastic resin composition of this embodiment can maintain an even higher level of balance between fluidity and impact resistance.

[0071] The terminal carboxyl group concentration of component (A-ba) is preferably 20 to 150 μmol / g, more preferably 30 to 130 μmol / g. By setting the terminal carboxyl group concentration within this range, the thermoplastic resin composition of this embodiment can maintain an even higher level of balance between fluidity and impact resistance.

[0072] The concentration of each end group of these polyamides can be adjusted by a known method, such as adding one or more compounds selected from diamine compounds, monoamine compounds, dicarboxylic acid compounds, and monocarboxylic acid compounds during polymerization of the polyamide so that the desired end group concentration is achieved.

[0073] The terminal amino group concentration and the terminal carboxyl group concentration can be measured by various methods. For example, １From the viewpoints of accuracy and simplicity, a method of determining the concentration of terminal groups from the integrated value of characteristic signals corresponding to each terminal group by H-NMR is preferred. For example, a specific example of a method for quantifying the terminal group concentration of a polyamide resin is the method described in the examples of JP-A-07-228689. Specifically, the number of each terminal group is １ From the viewpoint of accuracy and simplicity, it is preferable to determine the total number of molecular chain terminal groups from the integrated value of the characteristic signal corresponding to each terminal group by H-NMR (measured at 500 MHz in deuterated trifluoroacetic acid at 50°C). When the characteristic signal of the terminals blocked with the terminal blocking agent cannot be identified, the intrinsic viscosity [η] of the polyamide can be measured and the total number of molecular chain terminal groups can be calculated using the following relationship: Mn = 21900 [η] - 7900 (Mn represents the number average molecular weight) Total number of molecular chain terminal groups (eq / g) = 2 / Mn

[0074] In the (A-b-a) polyamide, it is preferable that 10 to 95% of the terminal groups of the molecular chain are blocked with a terminal blocking agent. The lower limit of the proportion of blocked terminal groups of the polyamide molecular chain (terminal blocking rate) is more preferably 40% or more, and even more preferably 60% or more. By setting the terminal blocking rate to the above lower limit or more, it is possible to suppress an increase in viscosity during molding of the thermoplastic resin composition of this embodiment. Furthermore, the upper limit of the terminal blocking rate is preferably 95% or less, and more preferably 90% or less. By setting the terminal blocking rate to the above upper limit or less, the impact resistance and the surface appearance of the molded article are further improved.

[0075] The terminal capping rate of a polyamide can be calculated by measuring the number of terminal carboxyl groups, terminal amino groups, and terminal groups capped with a terminal capping agent present in the polyamide, and then calculating the terminal capping rate (%) according to the following formula (1): Terminal capping rate (%) = [(α - β) / α] × 100 (1) (where α represents the total number of terminal groups in the molecular chain (unit: moles; this is usually equal to twice the number of polyamide molecules), and β represents the total number of terminal carboxyl groups and terminal amino groups (unit: moles) that remain uncapped.)

[0076] The end-capping agent is not particularly limited as long as it is a monofunctional compound reactive with the amino or carboxyl group at the polyamide terminal, but monocarboxylic acids and monoamines are preferred from the viewpoints of reactivity and stability of the blocked terminals, and monocarboxylic acids are more preferred from the viewpoints of ease of handling, etc. Other usable end-capping agents include acid anhydrides, monoisocyanates, monoacid halides, monoesters, and monoalcohols.

[0077] The monocarboxylic acid used as the end-capping agent is not particularly limited as long as it is reactive with an amino group, and examples thereof include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid; and any mixtures thereof. Among these, from the viewpoints of reactivity, stability of the blocked end, and economy, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, and benzoic acid are preferred, and acetic acid and benzoic acid are more preferred.

[0078] The monoamine used as the terminal blocking agent is not particularly limited as long as it is reactive with a carboxyl group, and examples thereof include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; and any mixtures thereof. Among these, from the viewpoints of reactivity, boiling point, stability of blocked terminals, and economy, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferred, and butylamine, hexylamine, and octylamine are more preferred.

[0079] For the purpose of further improving the heat resistance stability of the thermoplastic resin composition, a transition metal or a halogen may be present not only in the polyamide but also in the resin composition.

[0080] The type of transition metal is not particularly limited, and examples thereof include iron, copper, cerium, nickel, and cobalt. Among these, copper is preferred from the viewpoint of long-term thermal stability. The type of halogen is not particularly limited, but bromine and iodine are preferred from the viewpoint of preventing corrosion of production equipment and the like.

[0081] The transition metal content is preferably 1 ppm or more and less than 200 ppm, and more preferably 5 ppm or more and less than 100 ppm, by mass, when the total of Component (A-a) and Component (A-ba) of this embodiment is taken as 100 parts by mass. The halogen content is preferably 500 ppm or more and less than 1500 ppm, and more preferably 700 ppm or more and less than 1200 ppm, by mass, when the total of Component (A-a) and Component (A-ba) of this embodiment is taken as 100 parts by mass.

[0082] The method for adding these transition metals and halogens to the resin composition is not particularly limited, and examples thereof include a method of adding them as powder in the step of melt-kneading the polyamide and (A-a); a method of adding them during the polymerization of the polyamide; a method of producing master pellets of polyamide to which a high concentration of transition metal or halogen has been added, and then adding the master pellets of the polyamide to the resin composition, etc. Among these methods, the preferred methods are the method of adding them during the polymerization of the polyamide and the method of producing master pellets to which a high concentration of transition metal and / or halogen has been added to the polyamide, and then adding the master pellets.

[0083] In addition to the transition metals and / or halogens described above, known organic stabilizers can also be used without any problems in this embodiment.

[0084] Examples of the organic stabilizer include hindered phenol-based antioxidants such as Irganox 1098 (manufactured by Ciba Specialty Chemicals Co., Ltd.), phosphorus-based processing heat stabilizers such as Irgafos 168 (manufactured by Ciba Specialty Chemicals Co., Ltd.), lactone-based processing heat stabilizers such as HP-136 (manufactured by Ciba Specialty Chemicals Co., Ltd.), sulfur-based heat stabilizers, hindered amine-based light stabilizers, etc. Of these organic stabilizers, hindered phenol-based antioxidants, phosphorus-based processing heat stabilizers, or a combination thereof are more preferred.

[0085] The preferred amount of these organic stabilizers to be added is 0.001 to 1 part by mass per 100 parts by mass of the polyamide (Aba).

[0086] [(A-bb-b) Polypropylene Resin] The (A-bb-b) polypropylene resin is not particularly limited, and examples thereof include homopolymers and / or copolymers having propylene as a repeating unit structure, and preferred are crystalline propylene homopolymers, crystalline propylene-ethylene block copolymers, and mixtures of crystalline propylene homopolymers and crystalline propylene-ethylene block copolymers.

[0087] The crystalline propylene-ethylene block copolymer is not particularly limited, and examples thereof include those having a crystalline propylene homopolymer portion and a propylene-ethylene random copolymer portion.

[0088] The melt mass flow rate (hereinafter also referred to as "MFR") of the (A-bb) component is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more, and particularly preferably 0.5 g / 10 min or more, from the viewpoint of suppressing drawdown during combustion and improving the balance between fluidity and mechanical strength of the resin composition, and is preferably 15 g / 10 min or less, more preferably 6 g / 10 min or less, and particularly preferably 3 g / 10 min or less. Note that MFR can be measured in accordance with ISO 1133 under conditions of a temperature of 230°C and a load of 2.16 kg. Specifically, MFR can be measured by the method described in the Examples below.

[0089] The method for producing component (A-bb) is not particularly limited, and known methods can be used. Specific examples of methods for producing polypropylene include a method in which propylene is polymerized in the presence of a polymerization catalyst composition containing a titanium trichloride catalyst, a titanium halide catalyst supported on a carrier such as magnesium chloride, or the like, and an alkylaluminum compound, at a temperature of 0 to 100°C and a pressure of 3 to 100 atmospheres. In the above method, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the polymer.

[0090] In the above method, in addition to the polymerization catalyst composition, the polymerization system may further contain an electron donor compound as an internal donor component or an external donor component in order to enhance the isotacticity of the resulting polypropylene and the polymerization activity of the polymerization system. These electron donor compounds are not particularly limited, and known compounds can be used. Specific examples of electron donor compounds include ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate, and methyl toluate; phosphites such as triphenyl phosphite and tributyl phosphite; phosphoric acid derivatives such as hexamethylphosphoric triamide; alkoxyester compounds; aromatic monocarboxylic acid esters; aromatic alkylalkoxysilanes; aliphatic hydrocarbon alkoxysilanes; various ether compounds; various alcohols; and various phenols.

[0091] The polymerization method in the above method may be either a batch method or a continuous method, and the polymerization method may be solution polymerization or slurry polymerization using a solvent such as butane, pentane, hexane, heptane, or octane, or may be bulk polymerization in a monomer or gas phase polymerization in a gaseous polymer without a solvent.

[0092] Among the methods for producing component (A-bb), a method for producing a crystalline propylene-ethylene block copolymer is not particularly limited, and examples thereof include a method comprising: a first step of obtaining a crystalline propylene homopolymer portion; and a second step of copolymerizing the crystalline propylene homopolymer portion with ethylene and, if necessary, another α-olefin to obtain a propylene-ethylene block copolymer portion bonded to the crystalline propylene homopolymer portion. Examples of the other α-olefin include, but are not limited to, propylene, 1-butene, and 1-hexene.

[0093] The polypropylene resin may be a known modified polyolefin resin (grafted or added with 0.01 to 10% by weight of the α,β-unsaturated carboxylic acid or a derivative thereof) obtained by reacting a polyolefin resin with an α,β-unsaturated carboxylic acid or a derivative thereof in a molten or solution state at a temperature of 30 to 350°C in the presence or absence of a radical generator, or may be a mixture of the above-mentioned polypropylene resin and the modified polyolefin resin in any ratio.

[0094] The reason for using modified polyolefin resins is to improve the adhesion at the interface between the resin and the filler. By adding modified polyolefins, the adhesion at the interface between the resin and the filler improves, thereby increasing strength.

[0095] [Quantitative Ratio of (A-a) Polyphenylene Ether Resin to (A-bb-b) Polypropylene] In this embodiment, the preferred content ratio of the (A-a) component to the (A-bb-b) component is, when the total amount of the (A-a) component and the (A-bb-b) component is 100 parts by mass, the content of the (A-a) component is 10 to 70 parts by mass, and the content of the (A-bb-b) component is 30 to 90 parts by mass. More preferably, the content of the (A-a) component is 10 to 60 parts by mass, the content of the (A-bb-b) component is 40 to 90 parts by mass, and even more preferably, the content of the (A-a) component is 10 to 50 parts by mass, and the content of the (A-bb-b) component is 50 to 90 parts by mass. When the content ratio of the (A-a) component to the (A-bb-b) component is within this range, the balance of impact resistance, heat resistance, and tensile strength is excellent, and this is preferred.

[0096] The ratio of these components in the resin composition can be determined by a calibration curve method using Fourier transform infrared spectroscopy (FT-IR).

[0097] [(A-b-c) Polyphenylene sulfide resin] The (A-b-c) polyphenylene sulfide resin used in the present embodiment is divided into two types, a linear polyphenylene sulfide resin (hereinafter sometimes abbreviated as linear PPS) and a crosslinked polyphenylene sulfide resin (hereinafter sometimes abbreviated as crosslinked PPS), depending on the production method.

[0098] [[Linear PPS]] The former, linear PPS, is a polymer containing typically 50 mol % or more, preferably 70 mol % or more, and more preferably 90 mol % or more of arylene sulfide repeating units represented by the following chemical formula (1): [-Ar-S-] (1) (Here, Ar represents an arylene group, and examples of the arylene group include a p-phenylene group, an m-phenylene group, a substituted phenylene group (the substituent is preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group), a p,p'-diphenylenesulfone group, a p,p'-biphenylene group, a p,p'-diphenylenecarbonyl group, and a naphthylene group.)

[0099] Linear PPS may be a homopolymer containing one type of arylene group as a structural unit, or may be a copolymer obtained by mixing two or more different arylene groups from the viewpoints of processability and heat resistance. Among these, linear PPS containing p-phenylene sulfide repeating units as the main structural unit is preferred because of its excellent processability and heat resistance and ease of industrial availability.

[0100] This linear PPS is usually produced by polymerizing a halogen-substituted aromatic compound, such as p-dichlorobenzene, in the presence of sulfur and sodium carbonate; polymerizing in a polar solvent in the presence of sodium sulfide or sodium hydrogen sulfide and sodium hydroxide, or in the presence of hydrogen sulfide and sodium hydroxide or sodium aminoalkanoate; or by self-condensation of p-chlorothiophenol. Of these, the preferred method is to react sodium sulfide with p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide, or a sulfone solvent such as sulfolane.

[0101] These manufacturing methods are known, and linear PPS can be obtained by the methods described in, for example, U.S. Pat. No. 2,513,188, Japanese Patent Publication Nos. 44-27671, 45-3368, 52-12240, 61-225217, U.S. Pat. No. 3,274,165, Japanese Patent Publication No. 46-27255, Belgian Patent No. 29437, and Japanese Patent Publication No. 5-222196, as well as by the prior art methods exemplified in these documents.

[0102] A preferred linear PPS has an extractable amount with methylene chloride of 0.7% by mass or less, preferably 0.5% by mass or less, and a terminal -SX group (where S is a sulfur atom, and X is an alkali metal or hydrogen atom) content of 20 μmol / g or more, preferably 20 to 60 μmol / g.

[0103] The amount of methylene chloride extracted can be measured using the following method. 5 g of linear PPS powder is added to 80 mL of methylene chloride, and Soxhlet extraction is performed for 6 hours. The mixture is then cooled to room temperature, and the extracted methylene chloride solution is transferred to a weighing bottle. The container used for the extraction is then washed three times with a total of 60 mL of methylene chloride, and the washings are collected in the weighing bottle. The mixture is then heated to approximately 80°C to evaporate and remove the methylene chloride from the weighing bottle. The residue is then weighed, and the amount of methylene chloride extracted, i.e., the proportion of oligomers present in the linear PPS, can be determined from the amount of residue.

[0104] The amount of -SX groups can be quantified by the following method. Specifically, linear PPS powder is first dried at 120°C for 4 hours, and then 20 g of the dried linear PPS powder is added to 150 g of N-methyl-2-pyrrolidone and vigorously stirred and mixed at room temperature for 30 minutes to eliminate any powder agglomerates, resulting in a slurry. This slurry is then filtered and washed seven times, each time with 1 liter of warm water at approximately 80°C. The filter cake obtained here is reslurried in 200 g of pure water, and then 1 N hydrochloric acid is added to adjust the pH of the slurry to 4.5.

[0105] The mixture is then stirred at 25° C. for 30 minutes, filtered, and then washed six times with 1 liter of warm water at about 80° C. The resulting filter cake is reslurried in 200 g of pure water and then titrated with 1 N sodium hydroxide. The amount of —SX groups present in the linear PPS can be determined from the amount of sodium hydroxide consumed.

[0106] A specific example of a method for producing a linear PPS that satisfies the requirements of an extractable amount with methylene chloride of 0.7% by mass or less and a terminal -SX group content of 20 μmol / g or more is a method described in Japanese Patent Laid-Open No. 8-253587, in which an alkali metal sulfide and a dihaloaromatic compound are reacted in an organic amide solvent, and during the reaction, the gas phase in the reactor is cooled to condense part of the gas phase in the reactor, and this condense is refluxed into the liquid layer above the reaction solution, thereby reducing the oligomer components.

[0107] [[Crosslinked PPS]] Crosslinked (including semi-crosslinked) polyphenylene sulfide resins are produced by polymerizing the above-described linear PPS and then further heating it in the presence of oxygen at a temperature equal to or lower than the melting point of the polyphenylene sulfide resin to promote oxidative crosslinking and appropriately increase the polymer molecular weight and viscosity.

[0108] Among these crosslinked PPS, from the viewpoints of gas and resin generation during molding of the resin composition obtained by the present invention and of mold releasability, the most preferred is a crosslinked PPS having a volatile content of 1,000 ppm by mass or less collected in a molten state at 320° C. The volatile content collected in a molten state at 320° C. referred to here can be determined by the following method.

[0109] That is, 0.5 g of crosslinked PPS powder is weighed into a stoppered test tube having an airflow inlet and outlet, and immersed in a solder bath heated to 320°C for 30 minutes. While this is happening, nitrogen gas is injected into the test tube through the airflow inlet at a flow rate of 100 cc / min. Gas containing volatile components derived from the crosslinked PPS generated in the test tube is purged through the airflow outlet of the test tube. The purged gas is bubbled through the airflow inlet of a stoppered test tube containing acetone, which has an airflow inlet and outlet, into the acetone in the test tube, dissolving the volatile components in the acetone. The volatile components of the crosslinked PPS dissolved in acetone are analyzed using a gas chromatograph mass spectrometer (GC-MS) at a temperature increase from 50°C to 290°C. All components detected are quantified assuming the same sensitivity as monochlorobenzene, and the volatile components in the crosslinked PPS can be determined.

[0110] To obtain a crosslinked PPS with a volatile content of 1,000 ppm by mass or less when collected in a molten state at 320°C, the polymer concentration and solvent composition at the stage of polymerizing the linear PPS are usually devised, the washing method for recovering the polymer at the polymerization stage is devised, and the temperature and time of the high-temperature treatment at the subsequent crosslinking stage are changed. In this way, a crosslinked PPS with the desired volatile content can be obtained.

[0111] [Acid-Modified PPS] Furthermore, these PPSs (linear PPS, crosslinked PPS) may be acid-modified PPSs. Here, acid-modified PPS is obtained by modifying the above-mentioned PPS with an acid compound. Examples of such acid compounds include unsaturated carboxylic acids or their anhydrides, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and maleic anhydride, as well as saturated aliphatic carboxylic acids and aromatic-substituted carboxylic acids. Furthermore, inorganic acid compounds such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, and carbonic acid can also be used as such acid compounds.

[0112] [Melt Viscosity of PPS] The melt viscosity of the linear PPS and crosslinked PPS at 300° C. is preferably 1 to 10,000 Pa·s, more preferably 50 to 8,000 Pa·s, and even more preferably 100 to 5,000 Pa·s.

[0113] In the present specification, the melt viscosity refers to a value measured in accordance with JIS K-7210 as a reference test method using a flow tester (Model CFT-500 manufactured by Shimadzu Corporation) after preheating PPS at 300°C for 6 minutes under a load of 196 N and a die length (L) / die diameter (D) ratio of 10 mm / 1 mm.

[0114] [(Ac) Amorphous Thermoplastic Resin Other Than Polyphenylene Ether]

[0115] [[(A-ca) Polystyrene-based Resin]] The matrix resin (A) of this embodiment may contain a polystyrene-based resin. Examples of the polystyrene-based resin include atactic polystyrene, rubber-reinforced polystyrene (high impact polystyrene, HIPS), styrene-acrylonitrile copolymer (SAN) having a styrene content of 50% by weight or more, and ABS resin in which the styrene-acrylonitrile copolymer is rubber-reinforced. Atactic polystyrene and / or high impact polystyrene are preferred.

[0116] The polystyrene-based resins may be used alone or in combination of two or more. Note that the polystyrene-based resins do not include the styrene-glycidyl methacrylate copolymer (A-c-d) described below.

[0117] In the present embodiment, the content of the polystyrene-based resin (A-ca) is preferably 0 to 100 parts by mass, more preferably 0 to 90 parts by mass, and even more preferably 0 to 80 parts by mass, relative to 100 parts by mass of the polyphenylene ether-based resin (A-a).

[0118] [[(A-c-b) Block Copolymer Comprising at Least One Block Comprising Aromatic Vinyl Monomer Units and at Least One Block Comprising Conjugated Diene Monomer Units, and / or a Hydrogenated Product of the Block Copolymer]] In this embodiment, the composition may further comprise, and preferably comprises, (A-c-b) a block copolymer comprising at least one block comprising aromatic vinyl monomer units and at least one block comprising conjugated diene monomer units, and / or a hydrogenated product of the block copolymer (hereinafter, sometimes simply referred to as "component (A-c-b)"). In the present embodiment, (A-c-b) a block copolymer comprising at least one block mainly composed of aromatic vinyl monomer units and at least one block mainly composed of conjugated diene monomer units, and / or a hydrogenated product of the block copolymer, refers to a non-hydrogenated block copolymer comprising at least one aromatic vinyl polymer block mainly composed of aromatic vinyl monomer units and at least one conjugated diene polymer block mainly composed of conjugated diene monomer units, and / or a hydrogenated product of the block copolymer.

[0119] With regard to the aromatic vinyl polymer block, the phrase "mainly composed of aromatic vinyl monomer units" refers to a block in which aromatic vinyl monomer units account for 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and most preferably 90% by mass or more.

[0120] Similarly, the term "mainly composed of conjugated diene monomer units" of the conjugated diene polymer block refers to a block in which 50% by mass or more of conjugated diene monomer units are present, more preferably 70% by mass or more, even more preferably 80% by mass or more, and most preferably 90% by mass or more of conjugated diene monomer units.

[0121] The aromatic vinyl polymer block may be, for example, a copolymer block in which a small amount of a conjugated diene compound is randomly bonded to an aromatic vinyl polymer block. Similarly, the conjugated diene polymer block may be, for example, a copolymer block in which a small amount of an aromatic vinyl compound is randomly bonded to a conjugated diene polymer block.

[0122] The aromatic vinyl compound used to form the aromatic vinyl monomer unit 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, styrene is particularly preferred.

[0123] The conjugated diene compound used to form the conjugated diene polymer block 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.

[0124] The microstructure of the conjugated diene polymer block portion of the block copolymer preferably has a 1,2-vinyl content or the total amount of the 1,2-vinyl content and the 3,4-vinyl content (total vinyl bond amount) of 5 to 85%, more preferably 10 to 80%. The total vinyl bond amount can be measured using an infrared spectrophotometer.

[0125] The non-hydrogenated block copolymer used to produce the hydrogenated product of the block copolymer (hydrogenated block copolymer) is preferably a block copolymer in which the aromatic vinyl polymer block (A) and the conjugated diene polymer block (B) have a bonding type selected from A-B, A-B-A, and A-B-A-B. Among these, block copolymers having different bonding types may be used in combination. Among these, a bonding type selected from A-B-A and A-B-A-B is more preferred, and an A-B-A type bonding type is even more preferred.

[0126] Furthermore, the component (Acb) used in this embodiment is preferably a partially hydrogenated block copolymer (partially hydrogenated block copolymer).

[0127] The partially hydrogenated block copolymer is a block copolymer obtained by subjecting the above-described non-hydrogenated block copolymer to a hydrogenation treatment, thereby controlling the aliphatic double bonds in the conjugated diene polymer block to a range of more than 0% and less than 100%. The hydrogenation rate of the partially hydrogenated block copolymer is preferably 50% or more and less than 100%, more preferably 80% or more and less than 100%, and most preferably 98% or more and less than 100%.

[0128] Furthermore, the component (A-c-b) used in this embodiment preferably has a number average molecular weight of 30,000 or more but less than 300,000. When the molecular weight is within this range, a composition having excellent flowability, impact strength, and flame retardancy can be obtained.

[0129] The method for evaluating the number average molecular weight of the component (A-c-b) in the resin composition is described below. That is, the component (A-c-b) is separated using a solvent that is highly soluble in the component (A-c-b) but poorly soluble in the polyphenylene ether resin (A-a), such as chloroform. This is measured using a gel permeation chromatography measuring device [GPC SYSTEM21: manufactured by Showa Denko K.K.] and an ultraviolet spectrophotometer [UV-41: manufactured by Showa Denko K.K.], and the number average molecular weight is calculated using standard polystyrene. The measurement conditions may be as follows: solvent: chloroform, temperature: 40°C, column: sample side (K-G, K-800RL, K-800R), reference side (K-805L x 2), flow rate: 10 mL / min, measurement wavelength: 254 nm, pressure: 15 to 17 kg / cm ２ ) ]. When measuring the number average molecular weight, low molecular weight components may be detected due to catalyst deactivation during polymerization, but in such cases, the low molecular weight components are not included in the molecular weight calculation. The low molecular weight components refer to components with a molecular weight of 3,000 or less. Usually, the calculated correct molecular weight distribution (weight average molecular weight / number average molecular weight) is within the range of 1.0 to 1.1.

[0130] As for these block copolymers as component (A-c-b) that can be used in this embodiment, as long as it does not deviate from the spirit of this embodiment, two or more types of each of those having different bonding forms, different aromatic vinyl compound types, different conjugated diene compound types, different 1,2-bonded vinyl contents or different 1,2-bonded vinyl contents and 3,4-bonded vinyl contents, different aromatic vinyl compound component contents, different hydrogenation rates, etc. may be mixed and used.

[0131] Furthermore, the block copolymers usable as component (A-c-b) in this embodiment may be fully or partially modified block copolymers. The modified block copolymers referred to here refer to block copolymers modified with at least one modifying compound having, in the molecular structure, at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group.

[0132] The modified block copolymer can be produced, with or without a radical initiator, by (1) melt-kneading and reacting with a modifying compound in a temperature range from the softening point of the block copolymer to 250°C, (2) reacting the block copolymer with a modifying compound in a solution at a temperature below the softening point of the block copolymer, or (3) reacting the block copolymer with a modifying compound without melting at a temperature below the softening point of the block copolymer. 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. The "at least one modifying compound having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group in its molecular structure" referred to here can be the same modifying compound as described for the modified polyphenylene ether.

[0133] In the present embodiment, the content of the component (Ac-b) is preferably 1 to 40 parts by mass, more preferably 2 to 35 parts by mass, and even more preferably 2 to 30 parts by mass, relative to 100 parts by mass of the polyphenylene ether resin (Aa).

[0134] In addition, in this embodiment, from the viewpoint of being able to control the dielectric constant while maintaining a low dielectric loss tangent, the total content of the polyphenylene ether resin (A-a) and the component (A-c-b) relative to 100% by mass of the thermoplastic resin (A) is preferably 20% by mass or more, more preferably 25% by mass or more, and more preferably 30% by mass or more.

[0135] [[(A-cc) Ethylene-α-olefin Copolymer]] The thermoplastic resin composition of this embodiment may contain a copolymer of ethylene and an α-olefin other than ethylene (ethylene-α-olefin copolymer; hereinafter, sometimes simply referred to as the "(A-cc) component"). Here, from the viewpoint of the chemical resistance and impact resistance of the resulting resin composition, it is preferable that propylene units are not contained as monomer units constituting the (A-cc) component. Note that in the "olefin-based polymer composed of olefins," the phrase "not containing propylene units" also includes cases where propylene is contained as a structural unit to an extent that does not impair the effects of the invention. For example, it means that the content of propylene units in the (A-cc) component relative to all structural units constituting the (A-cc) component is less than 0.1% by mass.

[0136] Examples of the (A-cc) component include copolymers of ethylene and one or more C3 to C20 α-olefins. Among these, copolymers of ethylene and one or more C3 to C8 α-olefins are more preferred, copolymers of ethylene and one or more comonomers selected from the group consisting of 1-propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene are even more preferred, and copolymers of ethylene and 1-butene are particularly preferred. Using such copolymers as the (A-cc) component tends to result in resin compositions with higher impact properties and higher chemical resistance. The (A-cc) component may be used alone or in combination of two or more. Furthermore, two or more ethylene-α-olefin copolymers may be used as the (c) component.

[0137] From the viewpoint of flexibility of the resin composition, the ethylene content in the (Acc) component is preferably from 5 to 95% by mass, and more preferably from 30 to 90% by mass, based on the total amount of the olefin polymer.

[0138] The content of the α-olefin other than ethylene in the component (A-cc) is not particularly limited, but from the viewpoint of flexibility of the resin composition, it is preferably 5% by mass or more, and more preferably 20% by mass or more, relative to the total amount of the olefin-based polymer; and from the viewpoint of rigidity of the resin composition, it is preferably 50% by mass or less, and more preferably 48% by mass or less.

[0139] The brittle temperature of component (A-cc) is −50° C. or lower, and from the viewpoint of obtaining even better impact resistance and chemical resistance, it is preferably −60° C. or lower, and more preferably −70° C. or lower. The brittle temperature can be measured in accordance with ASTM D746.

[0140] [(A-c-d) Styrene-glycidyl methacrylate copolymer] The thermoplastic resin composition of the present embodiment may contain (A-c-d) styrene-glycidyl methacrylate copolymer (hereinafter, may be simply referred to as "component (A-c-d)"). Component (A-c-d) functions as a compatibilizer for the polyphenylene ether resin (A-a) and the polyphenylene sulfide resin (A-b-c).

[0141] The component (A-c-d) may contain other monomer components as long as it is a copolymer containing styrene and glycidyl methacrylate as monomer components, but is preferably a copolymer in which the total content of styrene-derived structures and glycidyl methacrylate-derived structures is 65 to 100 mass%, more preferably 75 to 100 mass%, and may even be 100 mass%.

[0142] Furthermore, the component (Acd) preferably contains a structure derived from glycidyl methacrylate in an amount of 0.3 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 3 to 10% by mass.

[0143] [(B) Inorganic Filler] In addition to the components described above, an inorganic filler can be added to the thermoplastic resin composition of this embodiment at any stage as needed. Adding an inorganic filler can suppress dimensional changes at high temperatures.

[0144] Examples of inorganic fillers include fibrous, granular, plate-like, or needle-like inorganic reinforcing materials such as glass fiber, potassium titanate fiber, gypsum fiber, brass fiber, ceramic fiber, boron whisker fiber, mica, talc, silica, calcium carbonate, kaolin, calcined kaolin, wollastonite, xonotlite, apatite, glass beads, glass flakes, and titanium oxide. Fillers with low anisotropy are particularly preferred. Two or more of these inorganic fillers can be used in combination. Among these, glass fiber, carbon fiber, and glass beads are more preferred. Furthermore, inorganic fillers that have been surface-treated by a known method using a surface treatment agent such as a silane coupling agent may also be used. However, natural mineral fillers often contain trace amounts of iron, so they must be purified to remove the iron.

[0145] A specific preferred content of each inorganic filler is 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or less, when the entire thermoplastic resin composition is taken as 100% by mass.

[0146] Furthermore, the total content of the inorganic filler is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, when the total thermoplastic resin composition is taken as 100% by mass.

[0147] [Colorant] In the present embodiment, there are no particular limitations on the method for coloring the resin composition, and one or more colorants selected from known organic dyes and pigments and inorganic pigments can be used.

[0148] Examples of organic dyes and pigments include azo pigments such as azo lake pigments, benzimidazolone pigments, diarylide pigments, and condensed azo pigments; phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; condensed polycyclic pigments such as isoindolinone pigments, quinophthalone pigments, quinacridone pigments, perylene pigments, anthraquinone pigments, perinone pigments, and dioxazine violet; azine pigments; and carbon black.

[0149] Among these, the carbon black should have a dibutyl phthalate (DBP) absorption of less than 250 mL / 100 g, preferably less than 150 mL / 100 g, and a nitrogen adsorption specific surface area of ​​900 m ２ / g, more preferably less than 400m ２ / g or less is preferable. When these values ​​are within this range, a composition that is particularly excellent in colorability, mechanical strength, and flame retardancy can be obtained. The DBP absorption amount and nitrogen adsorption specific surface area referred to here refer to values ​​measured by the methods specified in ASTM D2414 and JIS K6217, respectively. Examples of azine dyes include Solvent Black 5 (C.I. 50415, CAS No. 11099-03-9), Solvent Black 7 (C.I. 50415:1, CAS No. 8005-20-5 / 101357-15-7), and Acid Black 2 (C.I. 50420, CAS No. 8005-03-6 / 68510-98-5) in the Color Index.

[0150] Examples of inorganic pigments include metal oxides other than iron oxide, such as titanium oxide, zinc oxide, and chromium oxide, and composite metal oxides such as titanium yellow, cobalt blue, and ultramarine.

[0151] The preferred contents of the colorants are, when the entire resin composition is taken as 100% by mass, 2% by mass or less for carbon black, 2% by mass or less for azine dyes, and 8% by mass or less for inorganic pigments. More preferred amounts are 1% by mass or less for carbon black, 1% by mass or less for azine dyes, and 5% by mass or less for inorganic pigments. Adding these amounts allows a good balance between impact resistance and mechanical properties to be maintained. Furthermore, for applications requiring flame retardancy, the above amounts are preferred from the viewpoint of flame retardancy.

[0152] [(C) Other Components] In addition to the components described above, the resin composition of the present embodiment may contain, as other components (C), plasticizers (low-molecular-weight polyolefins, polyethylene glycol, fatty acid esters, etc.), antistatic agents, nucleating agents, flow improvers, reinforcing agents, various peroxides, spreading agents, copper-based heat stabilizers, organic heat stabilizers typified by hindered phenol-based antioxidants, antioxidants, ultraviolet absorbers, light stabilizers, lubricants such as ethylene bisstearamide, and modifying materials such as maleic anhydride.

[0153] The specific preferred content of each of the (C) other components is 15% by mass or less, more preferably 13% by mass or less, and even more preferably 10% by mass or less, when the entire resin composition is taken as 100% by mass.

[0154] Furthermore, the total content of (C) other components 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 total resin composition is 100% by mass.

[0155] <Characteristics of Thermoplastic Resin Composition> The characteristics of the thermoplastic resin composition of this embodiment will be described below.

[0156] The deflection temperature under load (DTUL) (°C) of the thermoplastic resin composition of this embodiment is preferably larger, from the viewpoint of being less susceptible to deformation even when the heat generated by base stations increases with the increase in communication speed. Specific DTUL values ​​are 120°C or higher, preferably 130°C or higher, and more preferably 140°C or higher. The deflection temperature under load (DTUL) refers to a value measured by the method described in the Examples below.

[0157] The thermoplastic resin composition of the present embodiment preferably has a smaller dielectric loss tangent, which indicates a reduced energy loss rate. The dielectric loss tangent is a value measured by the method described in the Examples below.

[0158] Furthermore, from the viewpoint of maintaining a low dielectric dissipation factor even when the heat generated by base stations increases as communication speeds increase, it is preferable that the temperature dependence of the dielectric dissipation factor at 28 GHz of the thermoplastic resin composition satisfies the following conditions: 1. When the DTUL is 120°C or higher but lower than 140°C, the difference between the dielectric dissipation factor at 23°C and the dielectric dissipation factor at 120°C is 0.004 or less; 2. When the DTUL is 140°C or higher, the difference between the dielectric dissipation factor at 23°C and the dielectric dissipation factor at 140°C is 0.004 or less. The temperature dependence of the dielectric dissipation factor tends to be able to be adjusted to within the above range by, for example, incorporating a thermoplastic resin having a low dielectric dissipation factor and a high glass transition temperature, such as (A-a) a polyphenylene ether resin, into the thermoplastic resin composition.

[0159] When the temperature of the thermoplastic resin composition used in the antenna member of this embodiment is divided into temperature ranges of 10°C increments as the temperature is increased from -30°C to 120°C, with the lower temperature side of two adjacent temperature ranges being the low temperature range and the higher temperature side being the high temperature range, the low temperature expansion coefficient (mm / mm / °C) of the thermoplastic resin composition in the TD direction, measured by the method specified in ISO 11359 in the low temperature range, and the high temperature expansion coefficient (mm / mm / °C) of the resin composition in the TD direction, measured by the method specified in ISO 11359 in the high temperature range, satisfy the following relationship in both of the two adjacent temperature ranges: -50≦((high temperature expansion coefficient−low temperature expansion coefficient) / low temperature expansion coefficient)×100≦50. This means that in antenna members molded by injection molding, the metal coating tends to be less susceptible to peeling due to temperature changes, and deformation of the component itself due to temperature changes can also be suppressed.

[0160] The above relationship is more preferably -45≦((high temperature expansion coefficient−low temperature expansion coefficient) / low temperature expansion coefficient)×100≦45, and even more preferably -40≦((high temperature expansion coefficient−low temperature expansion coefficient) / low temperature expansion coefficient)×100≦40.

[0161] The temperature range refers to 15 temperature ranges obtained by dividing the temperature range from -30°C to 120°C into -30°C to -20°C, -20°C to -10°C, -10°C to 0°C, ..., 110°C to 120°C. Furthermore, two adjacent temperature ranges refer to any of 14 combinations of two adjacent temperature ranges among the 15 divided temperature ranges. The above relationship is satisfied in all combinations (14 combinations) of two adjacent temperature ranges selected from the 15 divided temperature ranges. The coefficient of expansion in the TD direction of the resin composition measured by the method described in ISO 11359 refers to the value measured under the conditions described in the Examples below using a test piece prepared by the method described in the Examples below. By incorporating polyphenylene ether, an amorphous thermoplastic resin with a high glass transition temperature, into the thermoplastic resin composition, the variation in the coefficient of expansion between adjacent temperature ranges can be reduced, and the relationship between the coefficients of expansion can be adjusted.

[0162] The temperature is increased from -30°C to 120°C, and the temperature is divided into 15 sections at 10°C intervals. The average value of the expansion coefficient in the TD direction measured by the method described in ISO 11359 in each temperature range (the average value of the 15 expansion coefficient values, sometimes referred to as the "average expansion coefficient" in this specification) is 10 x 10 －５ mm / mm / °C or less, and more preferably 9 × 10 －５ mm / mm / °C or less, more preferably 8 x 10 －５ The average value can be set within the above range by using a resin with a low expansion coefficient and adjusting the type and amount of the inorganic filler. The thermoplastic resin composition of this embodiment has a maximum TD expansion coefficient of 10×10 or less, as measured by the method described in ISO 11359 in the temperature range obtained by dividing the temperature into 15 10°C intervals when increasing the temperature from -30°C to 120°C. －５ mm / mm / °C or less, and more preferably 2 × 10 －５ mm / mm / ℃~8×10 －５ mm / mm / °C. The maximum value is 10 x 10 －５When the expansion coefficient is less than 1 / mm / °C, large dimensional changes due to temperature rise can be suppressed, and peeling of the metal coating is less likely to occur. The maximum value can be kept within the above range by using a resin with a low expansion coefficient and adjusting the type and amount of inorganic filler, etc.

[0163] (Method for Producing Resin Composition) The resin composition of this embodiment can be produced by melt-kneading the components that make up the component (A), and further, if necessary, a colorant, an inorganic filler, and other components.

[0164] The melt kneader used for melt kneading is not limited to the following, but examples thereof include a single-screw extruder, a multi-screw extruder including a twin-screw extruder, a roll, a kneader, a Brabender Plastograph, a heated melt kneader such as a Banbury mixer, etc., and from the viewpoint of kneading properties, a twin-screw extruder is particularly preferred. Specific examples 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.

[0165] The melt-kneading temperature at this time can be selected to be a temperature equal to or higher than the melting point of the crystalline resin for a crystalline resin, or equal to or higher than the glass transition temperature of the amorphous resin, so that the resin can be heated and melted and processed without difficulty, and can usually be selected from the range of 200 to 370°C.

[0166] A preferred production method using an extruder is described below.

[0167] The L / D (effective barrel length / inner barrel diameter) of the extruder is preferably 20 or more and 60 or less, and more preferably 30 or more and 50 or less.

[0168] 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 further 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.

[0169] The method of supplying raw materials to the second to fourth raw material supply ports is not particularly limited, but a method of supplying raw materials from a side open port of the extruder using a forced side feeder is preferred because it tends to provide more stable supply than a method of simply adding raw materials through the open ports of the second to fourth raw material supply ports of the extruder.

[0170] In particular, when the raw materials contain powder and it is desired to reduce the generation of crosslinked products or carbonized products due to the thermal history of the resin, a method using a forced side feeder that supplies the raw materials from the side of the extruder is more preferable, and a method in which forced side feeders are provided at the second to fourth raw material supply ports and the raw material powder is supplied in portions is even more preferable.

[0171] When adding a liquid raw material, it is preferable to add it into the extruder using a plunger pump, gear pump or the like.

[0172] The upper openings of the second to fourth raw material supply ports of the extruder can also be used as openings for venting the air being transported.

[0173] The melt-kneading temperature and screw rotation speed in the melt-kneading step of the resin composition are not particularly limited, but can be selected so that the resin can be heated and melted without difficulty and processed at a temperature equal to or higher than the melting point of the crystalline resin for the crystalline resin, or at a temperature equal to or higher than the glass transition temperature of the amorphous resin for the amorphous resin. Typically, the temperature is selected arbitrarily from 200 to 370°C, and the screw rotation speed is set to 100 to 1200 rpm.

[0174] One specific example of a method for producing the resin composition of this embodiment using a twin-screw extruder is to supply the components constituting component (A) and the raw material titanium dioxide to the first raw material supply port of the twin-screw extruder, set the heat-melting zone to the melting temperature of the thermoplastic resin, and melt-knead the components at a screw rotation speed of 100 to 1200 rpm, preferably 200 to 500 rpm. Furthermore, the components constituting component (A) and the raw material titanium dioxide may be supplied to the twin-screw extruder all at once through the first raw material supply port, as described above, or the components may be supplied separately through second, third, and fourth raw material supply ports.

[0175] Furthermore, to reduce the generation of crosslinked products or carbonized materials due to the thermal history of the resin in the presence of oxygen, it is preferable to maintain the oxygen concentration of each process line in the route of adding each raw material to the extruder at less than 1.0% by volume. The above-mentioned addition route is not particularly limited, but a specific example may include a configuration in which, in order from a stock tank, a piping, a gravimetric feeder with a refill tank, a piping, a supply hopper, and a twin-screw extruder are used. 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. Usually, it is preferable to introduce nitrogen gas to maintain the oxygen concentration at less than 1.0% by volume.

[0176] When the thermoplastic resin in component (A) contains a powdery component (having a volume average particle size of less than 10 μm), the above-described method for producing a resin composition has the effect of further reducing residues in the screws of a twin-screw extruder when the resin composition of the present embodiment is produced using a twin-screw extruder, and further has the effect of reducing the generation of black spots, carbonized matter, and the like in the resin composition obtained by the above-described production method.

[0177] As a specific method for producing the resin composition of this embodiment, it is preferable to use an extruder in which the oxygen concentration at each raw material supply port is controlled to less than 1.0% by volume, and to carry out any one of the following methods 1 to 3.

[0178] 1. A production method in which the entire amounts of each component constituting component (A) contained in the resin composition of this embodiment are melt-kneaded (first kneading step), and the entire amount of raw titanium dioxide is supplied to the molten mixture obtained in the first kneading step, followed by melt-kneading (second kneading step). 2. A production method in which the entire amounts of each component constituting component (A) contained in the resin composition of this embodiment and a portion of the raw titanium dioxide are melt-kneaded (first kneading step), and the remaining amount of raw titanium dioxide is supplied to the molten mixture obtained in the first kneading step, followed by melt-kneading (second kneading step). 3. A method in which the entire amounts of each component contained in the resin composition of this embodiment are melt-kneaded.

[0179] In particular, some thermoplastic resins, such as (A-a) polyphenylene ether resins, contained in component (A), and raw material titanium dioxide, are powdery and have poor bite-into the extruder, making it difficult to increase the production volume per hour. Furthermore, the resin residence time in the extruder is long, making it prone to thermal degradation. For these reasons, the resin compositions obtained by the above-mentioned production methods 1 and 2 are more preferable than the resin composition obtained by production method 3, because they have improved bite-into titanium dioxide, excellent miscibility of the components, can reduce decomposition due to thermal degradation and the generation of crosslinked products and carbonized products, and can increase the production volume per hour of the resin, resulting in a resin composition with excellent productivity and quality.

[0180] [Injection Molded Article, Antenna Member] The injection molded article of this embodiment is made of the above-described thermoplastic resin composition. The method for producing the injection molded article of this embodiment is not particularly limited, except that it is injection molding. In the injection molding, injection foam molding can be performed to further reduce the weight. Both chemical foaming and physical foaming are effective and can contribute to weight reduction.

[0181] It is also envisaged that the injection-molded article produced by such a method may be used in a state in which a metal coating is formed on the surface thereof.

[0182] The antenna member of this embodiment includes one or more of the above-described injection molded articles. The antenna member may have a structure in which a plurality of molded articles are fitted together.

[0183] The antenna member of this embodiment has the injection-molded article, which makes it easy to apply to antenna components, particularly antenna filters, antenna elements (pendulums), and other components that require plating and are exposed to high temperatures. In particular, using a material whose expansion coefficient exhibits the relationship between the two adjacent temperature ranges specified in this embodiment is preferable because peeling and deformation of the metal coating when the temperature rises can be prevented.

[0184] [Metal Coating of Antenna Member] The method for metal coating at least a portion of the antenna member is not particularly limited, and conventionally known methods can be used. A metal coating can be formed on the insulating layer by dry plating or wet plating. In the case of wet plating, the surface of the injection-molded body is first roughened (etched) with an oxidizing agent such as permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, or nitric acid to form a roughened anchor. As the oxidizing agent, an aqueous solution of sodium hydroxide (alkaline permanganate aqueous solution) such as potassium permanganate or sodium permanganate is particularly preferred. Next, a metal coating is formed by a method combining electroless plating and electroplating. Alternatively, a plating resist with a reverse pattern to the desired metal coating can be formed, followed by electroless plating alone. Subsequent pattern formation methods, such as subtractive and semi-additive methods known to those skilled in the art, can be used.

[0185] Dry plating can be performed using known methods such as vapor deposition, sputtering, and ion plating. Examples of suitable methods include physical vapor deposition (PVD), chemical vapor deposition (CVD), and liquid phase growth. Examples of physical vapor deposition (PVD) methods include vacuum deposition, molecular beam epitaxy (MBE), sputtering, ionization deposition, laser ablation, and ion cluster beam deposition. Examples of chemical vapor deposition (CVD) methods include thermal CVD, plasma CVD, metalorganic CVD (MOCVD), chemical transport (CVT), and substrate reaction deposition. Examples of liquid phase growth methods include liquid phase epitaxy, traveling solvent deposition, and source current control. Other examples include electroless plating. Among the above methods, vacuum deposition, sputtering, and plasma CVD are preferred in terms of film thickness control, film quality control, versatility, and productivity.

[0186] The vacuum deposition method is a method in which a target for forming a film is heated and evaporated by an electron beam or a resistance heater to deposit a film on a substrate. The initial vacuum during deposition is set to 1×10 Pa or less, preferably 1×10 －３ After reducing the pressure to 0.5 Pa or less, it is preferable to carry out deposition at a rate of 0.5 to 100 Å / sec.

[0187] The sputtering method is a method in which high-kinetic energy particles such as argon ions supplied from a non-thermal equilibrium glow discharge plasma atmosphere or an ion beam from an ion source are collided with a target used for a film, resulting in emitted particles from the target, which are then deposited onto a substrate.

[0188] The plasma CVD method is a widely used method for forming hydrogenated amorphous silicon films. ４ This method involves decomposing a gas by high-frequency glow discharge to deposit a film on a substrate. The total pressure during discharge is 0.1 to 1 torr (13 to 130 Pa), the gas concentration when diluted with argon or hydrogen is 10% or more, the gas flow rate is 50 to 200 mL / min, and the input power is several tens to several hundreds of mW / cm. ２ is.

[0189] The metal used for the metal coating in this embodiment is not particularly limited, but it is preferable to use, for example, copper or gold, which have high electrical conductivity.

[0190] [Formation of Circuit on Antenna Member] The antenna member of this embodiment may be used after being coated with metal ink or plated.

[0191] The antenna member of this embodiment may have one or more selected from the group consisting of a metal circuit, a metal wiring, and a metal substrate.

[0192] From this viewpoint, an injection-molded article that can be coated with a metallic ink is preferably used as the injection-molded article of this embodiment. The metallic ink can be any of gold, silver, and copper. Furthermore, ink containing multiple metals can also be used.

[0193] The same applies to plating; any metal can be used. Copper is preferred from the viewpoint of electrical conductivity, but lead, tin, gold, and silver can also be used. The antenna member of this embodiment has high copper damage prevention properties and tends to have low water absorption, which can reduce cracking after application of the metal ink or plating.

[0194] For example, there are various methods for applying metal ink and then adhering it to the resin. Methods that require heat resistance, such as a method using a laser, can also be used with the antenna member of this embodiment.

[0195] For example, the circuit pattern of the wiring board can be formed by drawing a conductive metal paste onto the antenna member using an ink jet method, and this circuit pattern formation method may be a known method (see, for example, Japanese Patent Application Laid-Open No. 2002-324966).

[0196] The conductive metal paste used is a conductive metal paste obtained by uniformly dispersing ultrafine metal particles with a fine average particle size in a thermosetting resin composition containing an organic solvent, and the ultrafine metal particles have an average particle size selected in the range of 1 to 100 nm, and the surfaces of the ultrafine metal particles are preferably coated with one or more compounds having groups containing nitrogen, oxygen, or sulfur atoms as groups capable of forming coordinate bonds with the metal elements contained in the ultrafine metal particles.

[0197] The ultrafine metal particles having a small average particle size contained in the conductive metal paste are preferably fine particles made of one type of metal selected from the group consisting of gold, silver, copper, platinum, palladium, tungsten, nickel, tantalum, bismuth, lead, indium, tin, zinc, titanium, and aluminum, or fine particles of an alloy made of two or more types of metals.

[0198] The method for forming a circuit pattern includes the steps of spraying and applying the conductive metal paste as minute droplets onto a substrate to draw a circuit pattern consisting of a coating film of the conductive metal paste, and heat-treating the drawn coating film of the conductive metal paste at a temperature at least at which the thermosetting resin is thermally hardened.

[0199] Inkjet printing means include thermal printing means that generates bubbles by heating and foaming, and piezo printing means that ejects droplets by compression using a piezo element.

[0200] When forming a circuit by plating, there is a method that allows selective plating of copper, nickel, etc. on the laser irradiated area.

[0201] [Dielectric Properties of Antenna Member] The antenna member of this embodiment can be used in applications requiring a material with a low dielectric loss tangent, particularly in the high frequency range. In such applications, control of the dielectric loss tangent is an important technique, since high loss reduces the performance of the communication device member. This embodiment makes it possible to provide an injection-molded antenna member that exhibits little change in dimension or dielectric loss tangent at high temperatures while maintaining adhesion to the metal coating.

[0202] The antenna member of this embodiment can handle information of all frequencies, from low to high, and can therefore be used as a filter or antenna element (pendulum component) for an antenna for a communication device. In particular, because it maintains various properties and can demonstrate these properties even in low-temperature, high-temperature, or humid environments, it can be suitably used in heavy antenna base stations for outdoor or indoor use.

[0203] The present embodiment will be described in more detail below with reference to examples and comparative examples, but the present embodiment is not limited to these examples.

[0204] The raw materials and evaluation methods used in the examples and comparative examples are shown below.

[0205] [raw materials]

[0206] (A-a) Polyphenylene ether (hereinafter referred to as PPE) (A-a-1) Polyphenylene ether resin obtained by oxidative polymerization of 2,6-xylenol The reduced viscosity of the polyphenylene ether resin (0.5 g / dL, chloroform solution, measured at 30°C) was 0.52 dL / g. The Tg was approximately 210°C. (A-a-2) Polyphenylene ether resin obtained by oxidative polymerization of 2,6-xylenol The reduced viscosity of the polyphenylene ether resin (0.5 g / dL, chloroform solution, measured at 30°C) was 0.40 dL / g. The Tg was approximately 210°C. (A-a-3) Polyphenylene ether resin obtained by oxidative polymerization of 2,6-xylenol The reduced viscosity of the polyphenylene ether resin (0.5 g / dL, chloroform solution, measured at 30°C) was 0.32 dL / g. The Tg was about 210°C.

[0207] (A-b) Crystalline resin (A-ba) Polyamide

[0208] (A-b-a-1) Polyamide 6,6 (hereinafter, PA66) 2400 g of an equimolar salt of adipic acid and hexamethylenediamine, 100 g of adipic acid, and 2.5 liters of pure water were charged into a 5-liter autoclave and stirred thoroughly. After thoroughly replacing the atmosphere inside the autoclave with nitrogen, the temperature was raised from room temperature to 220°C over approximately 1 hour while stirring. During this time, the gauge pressure inside the autoclave reached 1.76 MPa due to natural pressure caused by water vapor. Heating was then continued while removing water from the reaction system so that the pressure did not exceed 1.76 MPa. After an additional 2 hours, when the internal temperature reached 260°C, heating was continued while the autoclave valve was opened and the internal pressure was reduced to 0.2 MPa over approximately 40 minutes. The mixture was then cooled to room temperature over approximately 8 hours. After cooling, the autoclave was opened, and approximately 2 kg of polymer was removed and pulverized. The polyamide obtained had a Mw of 38,700 and a Mw / Mn of 2.1. The Mw and Mn were determined using GPC (mobile phase: hexafluoroisopropanol, standard substance: PMMA (polymethyl methacrylate)). The terminal amino group concentration was measured according to the method described in the examples of JP-A-7-228689, and was found to be 38 μmol / g. The Tg was approximately 50°C.

[0209] (A-b-a-2) Polyamide 9,T (hereinafter referred to as PA9T) 9743.5g (58.65 mol) of terephthalic acid, 8027.8g (51.0 mol) of 1,9-nonanediamine, 1424.6g (9.0 mol) of 2-methyl-1,8-octanediamine, 329.7g (2.7 mol) of benzoic acid, 19.6g of sodium hypophosphite monohydrate (0.1% by mass based on the raw materials), and 5L of distilled water were placed in a 40L autoclave and purged with nitrogen. The mixture was stirred at 100°C for 30 minutes, and the internal temperature was raised to 210°C over 2 hours. At this time, the autoclave was pressurized to 22 kg / cm2. The reaction was continued for 1 hour, then the temperature was raised to 230°C, and the temperature was maintained at 230°C for 2 hours. The reaction was continued while gradually releasing water vapor to maintain the pressure at 22 kg / cm2. Next, the pressure was reduced to 10 kg / cm² over 30 minutes, and the reaction was continued for another hour, yielding a prepolymer with an intrinsic viscosity [η] of 0.25 dl / g. This was dried at 100°C under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This was subjected to solid-state polymerization at 230°C under 0.1 mmHg for 10 hours, and the melting point was 306°C and the intrinsic viscosity [η] was 0.80 dl / g. Furthermore, the terminal amino group concentration was measured according to the method for measuring terminal amino group concentration described in the examples of JP-A-7-228689, and was found to be 20 µmol / g. The Tg was approximately 125°C.

[0210] (A-bb-b) Polypropylene (A-bb-b-1) Polypropylene Polypropylene homopolymer with MFR = 2 g / 10 min. The MFR was measured in accordance with ISO 1133 at a temperature of 230°C and a load of 2.16 kg. The Tg was approximately 0°C. (A-bb-b-2) Polypropylene modified with maleic anhydride, with a number average molecular weight (Mn): 60,000 and a weight average molecular weight (Mw): 91,000. The Tg was approximately 0°C.

[0211] (A-b-c) Polyphenylene sulfide resins (A-b-c-1): A linear PPS having a melt viscosity (measured using a flow tester at 300°C, a load of 196 N, and an L / D ratio of 10 / 1 after 6 minutes) of 30 Pa·s, an extractable amount with methylene chloride of 0.7 mass%, and a repeating unit of p-phenylene sulfide with an -SX group content of 32 μmol / g. The Tg was approximately 80°C. (A-b-c-2): A crosslinked PPS having a melt viscosity (measured using a flow tester at 300°C, a load of 196 N, and an L / D ratio of 10 / 1 after 6 minutes) of 60 Pa·s and a volatile content of 160 ppm by mass collected in a molten state at 320°C. The Tg was approximately 80°C.

[0212] (A-c) Amorphous thermoplastic resin other than polyphenylene ether

[0213] (A-ca) Polystyrene Resins (A-ca-1) High impact polystyrene (H9405 manufactured by PS Japan Co., Ltd.) Tg was about 100°C. (A-ca-2) High impact polystyrene (trade name "CT-60" manufactured by Petrochemicals Co., Ltd.) Tg was about 100°C. (A-ca-3) Polystyrene (GPPS 680 manufactured by PS Japan Co., Ltd.) Tg was about 100°C.

[0214] (A-c-b) A block copolymer comprising at least one block mainly composed of aromatic vinyl monomer units and at least one block mainly composed of conjugated diene monomer units, and / or a hydrogenated product of the block copolymer. (A-c-b-1) Hydrogenated block copolymer (Tuftec (trademark) H1051, manufactured by Asahi Kasei Corporation) (A-c-b-2) Hydrogenated block copolymer (Tuftec (trademark) H1081, manufactured by Asahi Kasei Corporation) (A-c-b-3) A block copolymer having a II-I-III-I block structure was synthesized by a known method, with polymer block I consisting of polystyrene and polymer block II consisting of polybutadiene. The synthesized block copolymer was hydrogenated by a known method. The polymer was not modified. The physical properties of the obtained unmodified hydrogenated block copolymer are shown below. Polystyrene content in block copolymer after hydrogenation: 44% by mass, number average molecular weight (Mn) of block copolymer after hydrogenation: 95,300, weight average molecular weight (Mw): 113,600, 1,2-vinyl bond amount (total vinyl bond amount) in polybutadiene block after hydrogenation: 79%, hydrogenation rate relative to polybutadiene portion constituting polybutadiene block: 99% (A-c-b-4) Styrene-ethylene-propylene-styrene block copolymer elastomer (Septon 2023, manufactured by Kuraray Co., Ltd.)

[0215] (A-cc) Ethylene-α-olefin copolymer (A-cc-1) Ethylene-α-olefin copolymer (Tafmer P-0680J, manufactured by Mitsui Chemicals, Inc.)

[0216] (A-c-d) Styrene-glycidyl methacrylate copolymer (A-c-d-1) Styrene-glycidyl methacrylate copolymer containing 5% by mass of glycidyl methacrylate (weight average molecular weight: 110,000) (A-c-e) Thermoplastic norbornene resin (A-c-e-1) Thermoplastic norbornene resin (ZEONEX480, manufactured by Nippon Zeon Co., Ltd.) Tg was approximately 140°C.

[0217] (B) Inorganic filler (B-1) Glass fiber (ECS03-T249 manufactured by Nippon Electric Glass Co., Ltd.) (B-2) Glass fiber (ECS03-T747 manufactured by Nippon Electric Glass Co., Ltd.) (B-3) Glass fiber (ECS03-T497 manufactured by Nippon Electric Glass Co., Ltd.) (B-4) Talc (Hitron A manufactured by Takehara Chemical Industry Co., Ltd.) (B-5) Talc (Talc Powder PK-C manufactured by Hayashi Chemical Industry Co., Ltd.) (B-6) Glass flakes (Fleka REFG-301 manufactured by Nippon Sheet Glass Co., Ltd.) (B-7) Glass flakes (MEG160FY M06 manufactured by Nippon Sheet Glass Co., Ltd.)

[0218] (Other Components) (C-1) Ethylenebisstearamide ("Kaowax EB-G" manufactured by Kao Corporation) (C-2) Maleic anhydride ("Crystal MAN" manufactured by NOF Corporation) (C-3) Peroxide ("Perhexa 25B-40" manufactured by NOF Corporation)

[0219] [Evaluation Method] The evaluation tests carried out in the examples and comparative examples were carried out as follows.

[0220] (1-1), (1-2) Dielectric constant and dielectric loss tangent at 1 GHz The obtained resin composition pellets were fed into a small injection molding machine (product name: EC75-SXII, manufactured by Toshiba Machine Co., Ltd.) with a cylinder temperature set to 250 to 350°C, and a 60 mm x 60 mm x 2.0 mm plate was produced under the following conditions: mold temperature 70 to 130°C, injection pressure 200 MPa, injection time 20 seconds, and cooling time 15 seconds. The plate was also cut and measured under the following conditions. Measurement equipment: Vector Network Analyzer HP8510C (Agilent Technologies) Synthesized Sweeper HP83651A (same as above) Test Set HP8517B (same as above) Test piece dimensions: 40 mm x 4 mm x 2.0 mm Resonator shape: Cylinder with inner diameter 229 mm and height 40 mm Measurement direction: One direction Measurement frequency: Near 1 GHz (TM010 mode) Pretreatment: 90 h / 22 ± 1 ° C / 60 ± 5% RH Test environment: 22 ° C / 56% RH It was determined that the lower the dielectric dissipation factor, the better the performance. (1-3), (1-4) Dielectric constant and dielectric loss tangent at 28 GHz The obtained resin composition pellets were fed into a small injection molding machine (product name: EC75-SXII, manufactured by Toshiba Machine Co., Ltd.) set at a cylinder temperature of 250 to 350°C, and a 150 mm x 150 mm x 4.0 mm flat plate was produced under the conditions of a mold temperature of 70 to 130°C, an injection pressure of 200 MPa, an injection time of 20 seconds, and a cooling time of 20 seconds, and the dielectric constant at 28 GHz was measured under the following conditions. Measurement frequency: 22 GHz to 33 GHz Measurement method: frequency change method Measurement equipment: vector network analyzer (Keysight PNA N5247B 10 MHz to 67 GHz), Keycom high frequency free space type S parameter measurement jig, control PC Measurement environment conditions: room temperature 26°C, humidity 50% (1-5) Dielectric loss tangent after water absorption The obtained resin composition pellets were supplied to a small injection molding machine (product name: EC75-SXII, manufactured by Toshiba Machine Co., Ltd.) with a cylinder temperature set to 250 to 350°C, and a 60 mm x 60 mm x 0.9 mm flat plate was produced under conditions of a mold temperature of 70 to 130°C, an injection pressure of 200 MPa, an injection time of 20 seconds, and a cooling time of 20 seconds. This was immersed in 80°C hot water for 144 hours, and then the dielectric loss tangent at 10 GHz was measured under the following conditions.Measurement frequency: 10GHz Measurement equipment: 10MHz to 43.5GHz PNA network analyzer N5224B, 10GHz Split Post Dielectric Resonator N1501AE10 Measurement environmental conditions: Room temperature 23℃, humidity 50%.

[0221] (2) Deflection Temperature Under Load (DTUL) Pellets of the obtained resin composition were fed into a small injection molding machine (product name: EC75-SXII, manufactured by Toshiba Machine Co., Ltd.) set at a cylinder temperature of 250 to 350°C, and ISO dumbbells for evaluation were produced using conditions and molds conforming to ISO dumbbell molding conditions, with a mold temperature of 70 to 130°C, an injection pressure of 200 MPa, an injection time of 20 seconds, and a cooling time of 15 seconds. The ISO dumbbells were then cut to produce test pieces for measuring the deflection temperature under load (DTUL). The deflection temperature under load (DTUL) was measured using the test pieces for measuring the deflection temperature under load (ISO 75: 1.80 MPa load). It was determined that the larger the value, the better the heat resistance.

[0222] (3) Plating Ability Pellets of the resulting resin composition were fed into a small injection molding machine (product name: EC75-SXII, manufactured by Toshiba Machine Co., Ltd.) set at a cylinder temperature of 250 to 350°C. A 90 mm x 50 mm x 2.5 mm flat plate was fabricated under the following conditions: a mold temperature of 70 to 130°C, an injection pressure of 200 MPa, an injection time of 20 seconds, and a cooling time of 15 seconds. The flat plate was then etched with chromic acid and electroless copper plating was performed. A ◯ was indicated if the entire flat plate was plated, and an × was indicated if the plate was not plated. The plate with the highest plating coverage was judged to be superior as a communication device component. Furthermore, the plate was subjected to a heat cycle test between -30°C and 85°C for 30 cycles, each lasting 60 minutes. After cutting the × mark with a cutter, a peel test was performed using Cellophane® tape. At this time, if the plating did not peel off visually, it was marked with a circle, and if the plating peeled off visually, it was marked with an X, and the less peeling there was, the better the part was judged to be for use in communication devices. Whether the plating had peeled off was judged by applying Cellophane (registered trademark) tape and checking whether the resin surface was visible over 10% or more of the peeled area (100%).

[0223] (4) Temperature Dependence of Dielectric Loss Tangent at 28 GHz Pellets of the obtained resin composition were fed into a small injection molding machine (product name: EC75-SXII, manufactured by Toshiba Machine Co., Ltd.) with a cylinder temperature set to 250 to 350°C, and a 60 mm x 60 mm x 0.9 mm flat plate was produced under the following conditions: mold temperature 70 to 130°C, injection pressure 250 MPa, injection time 20 seconds, and cooling time 15 seconds. The flat plate was cut to 37 mm x 37 mm x 0.9 mm, and the dielectric loss tangent was measured using the following device. At this time, for materials with a DTUL of 120°C or higher and 140°C or lower, the dielectric loss tangent at 23°C was compared with the dielectric loss tangent at 120°C. For materials with a DTUL of 140°C or higher, the dielectric loss tangent at 23°C was compared with the dielectric loss tangent at 140°C. The smaller the difference between these values, the better the material was judged to be for use in communication equipment. Measurement equipment: Keysight Technologies N5227B PNA microwave network analyzer 67 GHz Resonator: FATEC balanced disc resonator Thermostat: Espec SU-662

[0224] (5) Expansion Coefficient The pellets of the obtained resin composition were fed into a small injection molding machine (product name: EC75-SXII, manufactured by Toshiba Machine Co., Ltd.) with a cylinder temperature set to 250 to 350 ° C., and an ISO dumbbell for evaluation was produced using conditions and a mold conforming to the ISO dumbbell molding conditions: a mold temperature of 70 to 130 ° C., an injection pressure of 200 MPa, an injection time of 20 seconds, and a cooling time of 15 seconds. Also, a test piece was cut out from the ISO dumbbell as shown in FIG. 1, and after standing for 168 hours in a laboratory regulated at a temperature of 23 ° C. and a humidity of 50% RH, the expansion coefficient was measured under the following conditions using a thermomechanical analyzer (TMA, product name TMA / SS6100, manufactured by SII Technology Co., Ltd.) according to the method described in ISO 11359.

[0225] After annealing at 100°C for 4 hours, the specimen was cooled to -40°C under a nitrogen atmosphere (flow rate 100 ml / min) with a compressive load of 3 gf, and then heated to 150°C at a rate of 5°C / min, and the TD expansion coefficient was measured. The expansion coefficient was measured in 10°C intervals (15 temperature ranges) from -30°C to 120°C. The highest value of the expansion coefficients in the 15 temperature ranges was taken as the maximum expansion coefficient (mm / mm / °C), and the average value of the expansion coefficients in the 15 temperature ranges was calculated as the average expansion coefficient (mm / mm / °C). Furthermore, when the lower temperature side of any two adjacent temperature ranges among the 15 temperature ranges was defined as the low temperature range and the higher temperature side was defined as the high temperature range, the rate of change in the expansion coefficient between the low temperature range and the high temperature range was calculated using the expansion coefficient of the low temperature range (low temperature range expansion coefficient (mm / mm / °C)) and the expansion coefficient of the high temperature range (high temperature range expansion coefficient (mm / mm / °C)) using the following formula, and the value with the largest rate of change was defined as the maximum rate of change (%). (Rate of change in expansion coefficient between low temperature range and high temperature range) = (expansion coefficient in high temperature range - expansion coefficient in low temperature range / expansion coefficient in low temperature range) x 100 Any two adjacent temperature ranges mentioned above refer to 14 combinations of adjacent temperature ranges (for example, a combination of a low temperature range from -30°C to -20°C and a high temperature range from -20°C to -10°C, a combination of a low temperature range from -20°C to -10°C and a high temperature range from -10°C to 0°C) obtained by dividing the temperature range from -30°C to 120°C into 15 ranges of 10°C each (-30°C to -20°C, -20°C to -10°C, -10°C to 0°C, ... 110°C to 120°C).

[0226] (6) Antenna efficiency at high and low temperatures The antenna efficiency was simulated under the following conditions: Antenna substrate: 60 x 7 x 1 mm 3 , Fully grounded, pattern width 1mm, thickness 25μm. Copper + Ni plating Main board: 60 × 130 × 1mm 3 , relative permittivity 4.0, dielectric loss 0.020, thickness 35 μm, conductivity 5.8 × 10 7S / m Simulation equipment: CST MW STUDIO. Adjusted so that the reflection coefficient was 6 dB or less in the operating frequency band. Dielectric properties of materials (dielectric constant and dielectric loss tangent) The dielectric properties of materials were measured using method (4). <High temperature range> The following values ​​were used depending on the DTUL value of the material. For materials with a DTUL of 120°C or less, the dielectric properties at 100°C. For materials with a DTUL of 120°C to 140°C, the dielectric properties at 120°C. For materials with a DTUL of 140°C or more, the dielectric properties at 140°C. <Low temperature range> The dielectric properties at -30°C were used. Then, the total efficiency at 4 GHz was obtained from the simulation, and this total efficiency was used as the antenna efficiency. The closer the total efficiency is to 0, the better, and it can be said that the antenna performance is high.

[0227] [Examples 1 to 13, Comparative Examples 1 to 5] (A) Thermoplastic resin and other components were blended according to the composition shown in Table 1, and a resin composition was produced using a twin-screw extruder ZSK-40 (manufactured by COPERION WERNER & PFLEIDERER, Germany). In this twin-screw extruder, a first raw material supply port was provided upstream of the raw material flow direction, a first vacuum vent was provided downstream of this, a second raw material supply port was provided midstream, a third raw material supply port was provided downstream of this, and a second vacuum vent was provided further downstream. Using the extruder configured as described above, each component was added according to the composition and addition method shown in Tables 1 and 2, and melt-kneaded under conditions of an extrusion temperature of 250 to 320°C, a screw rotation speed of 300 rpm, and a discharge rate of 100 kg / hour to produce pellets. The resulting resin composition pellets were used for the above-mentioned evaluations. The evaluation results are shown in Tables 1 and 2.

[0228]

[0229] The antenna member of the present invention can be suitably used in antenna filters, antenna elements (pendulums), etc., and has industrial applicability. In particular, it can be suitably used as an antenna member that maintains adhesion to a metal coating while exhibiting little change in dimension or dielectric loss tangent at high temperatures, is molded by injection molding, and is applicable to all environments, including low temperatures, high temperatures, and humidity.

Claims

1. An antenna member having an injection molded body made of a thermoplastic resin composition, wherein at least a part of the injection molded body is used with a metal coating, The thermoplastic resin composition contains (A) a thermoplastic resin, and the (A) thermoplastic resin contains (A-a) a polyphenylene ether resin, 3. When raising the temperature of the thermoplastic resin composition from -30°C to 120°C, the temperature is divided into temperature ranges every 10°C, and the average value of the linear expansion rate in the TD direction of the resin composition, measured in accordance with ISO 11359 for each temperature range, is 10×10 －５ mm / mm / °C or less. The antenna member according to claim 1 or 2.

4. When raising the temperature of the thermoplastic resin composition from -30°C to 120°C, the temperature is divided into temperature ranges every 10°C, and among the linear expansion rates in the TD direction of the resin composition measured in accordance with ISO 11359 for each temperature range, the maximum value is 10×10 －５ mm / mm / °C or less. The antenna member according to claim 3. The heat deflection temperature (DTUL) of the thermoplastic resin composition is 120° C. or higher, When the temperature of the thermoplastic resin composition is increased from -30° C. to 120° C. and divided into temperature ranges every 10° C., with the low temperature side of two adjacent temperature ranges being the low temperature range and the high temperature side being the high temperature range, the low temperature range expansion rate (mm / mm / ° C.) in the TD direction of the resin composition measured by the method described in ISO 11359 in the low temperature range and the high temperature range expansion rate (mm / mm / ° C.) in the TD direction of the resin composition measured by the method described in ISO 11359 in the high temperature range satisfy the following relationship in any two adjacent temperature ranges. -50 ≦ ((high temperature range linear expansion rate - low temperature range linear expansion rate) / low temperature range linear expansion rate) × 100 ≦ 50 2. The antenna member according to claim 1, wherein the temperature dependence of the dielectric loss tangent of the thermoplastic resin composition at 28 GHz satisfies the following conditions.

1. When DTUL is 120° C. or higher and less than 140° C., the difference between the dielectric loss tangent at 23° C. and the dielectric loss tangent at 120° C. is 0.004 or less.

2. When DTUL is 140° C. or higher, the difference between the dielectric loss tangent at 23° C. and the dielectric loss tangent at 140° C. is 0.004 or less.

5. The antenna member according to claim 1 or 2, wherein the (A) thermoplastic resin contains (A-b) a crystalline resin.

6. The antenna member according to claim 1 or 2, wherein the thermoplastic resin composition contains 10% by mass or more of (B) an inorganic filler.

7. The antenna member according to claim 1 or 2, wherein the (A) thermoplastic resin contains 10% by mass or more of (A-a) a polyphenylene ether resin.

8. The antenna member according to claim 1 or 2, which is used for an outdoor or indoor antenna base station.

9. The antenna member according to claim 1 or 2, having a metal coating formed by electroless copper plating with chromic acid etching.

10. The antenna member according to claim 1 or 2, wherein after forming a metal coating by electroless copper plating with chromic acid etching and leaving it at 85° C. and 85% humidity for 2000 h, no cracks occur in the metal layer.

11. The antenna member according to claim 1 or 2, wherein the thermoplastic resin composition contains a (A-c-a) polystyrene-based resin.

12. The antenna member according to claim 1 or 2, wherein the thermoplastic resin composition contains at least one block mainly composed of an aromatic vinyl monomer unit and at least one block mainly composed of a conjugated diene monomer unit, and / or a hydrogenated product of the block copolymer.

13. The antenna member according to claim 1 or 2, which is an antenna filter.

14. The antenna member according to claim 1 or 2, which is an antenna element.