Antenna components

Abstract

This invention relates to an antenna component having an injection-molded body composed of a thermoplastic resin composition. The antenna component is used by metallizing at least a portion of the injection-molded body. The thermoplastic resin composition comprises a polyphenylene ether resin. The load flexural temperature of the thermoplastic resin composition is 120°C or higher. The temperature of the thermoplastic resin composition when the temperature is increased from -30°C to 120°C is divided into temperature regions spaced 10°C apart. When the lower temperature side of two adjacent temperature regions is designated as the low-temperature region and the higher temperature side as the high-temperature region, the expansion rates of the low-temperature region and the high-temperature region, measured using the method described in ISO 11359, satisfy the following relationship in any two adjacent temperature regions: -50 ≤ ((expansion rate of high-temperature region - expansion rate of low-temperature region) / expansion rate of low-temperature region) × 100 ≤ 50.

Description

Technical Field

[0001] This invention relates to antenna components. Background Technology

[0002] In the past, antenna components have been made using a large amount of metal and ceramics to ensure mechanical performance and heat resistance. However, especially in base stations for communication equipment, there is a pressing need for lightweight construction due to the requirements for ease of installation and ease of assembly, leading to a demand for resin-based components.

[0003] For example, filters made of metal or ceramic require multiple surfaces to be coated with metal to filter radio waves. When resin is used instead, a resin that can be coated using plating or sputtering is required. Furthermore, antenna elements (vibrators) in communication devices can perform as antennas by drawing metal circuits on resin with a low dielectric loss tangent.

[0004] On the other hand, as surface-mount dielectric antennas used in mobile communication devices such as mobile phones or wireless LANs, antennas composed of dielectric ceramic monomers, resin monomers, and resin compositions containing ceramics have been proposed. For example, the following solutions are disclosed: a surface-mount dielectric antenna whose antenna substrate is composed of ceramic monomers or resin monomers (see Patent Document 1); a foam body composed of a styrene-based resin with good plating properties and a dielectric constant of approximately 18, and a method for manufacturing the same (see Patent Document 2). The following solutions are also disclosed: a resin composition made by mixing spherical dielectric ceramic powder in a resin material at a proportion of 40 vol% to 70 vol% (volume %) (in the composition) (see Patent Document 3); a composite material made by adjusting the aspect ratio of titanate metal salt fibers to 3 to 5 to achieve high filling, and combining them with thermoplastic resins, etc. (see Patent Document 4).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 9-98015

[0008] Patent Document 2: Japanese Patent Application Publication No. 10-45936

[0009] Patent Document 3: Japanese Patent No. 3930814

[0010] Patent Document 4: Japanese Patent No. 2992667 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] When using resin compositions in antenna components like those described above, excellent mechanical properties, electrical properties, heat resistance, and dimensional stability are required. Furthermore, for ease of molding into the desired shape, injection molding is preferred. Additionally, materials capable of metallization by plating or sputtering, and whose metallization does not peel off at high temperatures, are required. Specifically, heat is generated in any component during communication, thus requiring the resin itself to have high heat resistance, minimal dimensional changes even in high-temperature regions, and no peeling of the metallization. Antennas are exposed to the external environment and may become internally hot due to the presence of heat-dissipating components. Antenna characteristics must be maintained even at high temperatures, requiring materials with low dielectric constants and dielectric loss tangents even at high temperatures. Furthermore, resins capable of forming circuits are required; from a circuit formation perspective, materials exhibiting antenna characteristics in high-frequency bands above 1 GHz and maintaining low dielectric loss tangents even in high-temperature regions are required.

[0013] Furthermore, with the widespread adoption of 5G communication in recent years, there is a growing demand for communication base stations capable of 5G communication. As communication speeds increase, base stations generate more heat, necessitating very heavy heat sinks to dissipate it, significantly increasing the overall weight and raising the requirements for lightweight design. In particular, antenna filters, made of metal or ceramic, account for a considerable portion of the base station's weight. While resin-coating antenna filters can achieve weight reduction and simplify manufacturing processes, it requires the fabrication of a metal coating, presenting challenges in maintaining the tight seal between the resin and metal. Additionally, in the antenna element, not only is a tight seal between the resin and metal required due to the need for metal-based circuitry, but materials with low dielectric loss tangent are also essential for optimal antenna performance. This increasing sophistication of communication necessitates the ability to handle information at all frequencies, from low to high.

[0014] Furthermore, with the widening of communication areas in recent years, antenna components, while maintaining the aforementioned characteristics, are also required to perform these characteristics even in low-temperature, high-temperature, or humid environments.

[0015] Therefore, the purpose of this invention is to provide an antenna component that can maintain a tight fit with a metal coating, while exhibiting small dimensional changes and dielectric loss tangent changes in high-temperature regions, can be formed by injection molding, and is applicable in all environments such as low temperature, high temperature, and humidity.

[0016] Methods for solving problems

[0017] In order to solve the above problems, the inventors conducted in-depth research and found that by using a specific resin composition for antenna components, antenna performance can be maintained in all environments, while also contributing to the lightweighting of communication equipment and the simplification of assembly processes, thus realizing the present invention.

[0018] That is, the present invention is as follows. [1]

[0020] An antenna component comprising an injection-molded body made of a thermoplastic resin composition, wherein at least a portion of the injection-molded body is metal-coated for use, wherein...

[0021] The above thermoplastic resin composition comprises (Aa) polyphenylene ether resin.

[0022] The above-mentioned thermoplastic resin composition has a load flexural temperature (DTUL) of 120°C or higher.

[0023] The temperature of the thermoplastic resin composition when the temperature is increased from -30°C to 120°C is divided into temperature regions with intervals of 10°C. When the lower temperature side of two adjacent temperature regions is designated as the low temperature region and the higher temperature side as the high temperature region, in any of the two adjacent temperature regions, the expansion rate (mm / mm / °C) of the resin composition in the TD direction in the low temperature region, measured using the method described in ISO 11359, and the expansion rate (mm / mm / °C) of the resin composition in the TD direction in the high temperature region, measured using the method described in ISO 11359, both satisfy the following relationship.

[0024] -50≦((expansion rate of high temperature region - expansion rate of low temperature region) / expansion rate of low temperature region)×100≦50 [2]

[0026] The antenna component as described in [1], wherein the temperature dependence of the dielectric loss tangent of the above thermoplastic resin composition at 28 GHz satisfies the following conditions.

[0027] Condition 1: When the DTUL is above 120℃ and below 140℃, the difference between the dielectric loss tangent at 23℃ and the dielectric loss tangent at 120℃ is less than 0.004.

[0028] Condition 2: When the DTUL is above 140°C, the difference between the dielectric loss tangent at 23°C and the dielectric loss tangent at 140°C is less than 0.004. [3]

[0030] The antenna component as described in [1] or [2], wherein the temperature of the thermoplastic resin composition when the temperature is increased from -30°C to 120°C is divided into temperature zones with intervals of 10°C, and the average value of the expansion rate of the resin composition in the TD direction, measured by the method described in ISO 11359, for each temperature zone is 10 × 10⁻⁶.-5 Below mm / mm / ℃. [4]

[0032] The antenna component described in [3] is wherein the temperature of the thermoplastic resin composition when the temperature is increased from -30°C to 120°C is divided into temperature zones with intervals of 10°C, and the maximum value of the expansion rate of the resin composition in the TD direction, measured by the method described in ISO 11359, in each temperature zone is 10 × 10⁻⁶. -5 Below mm / mm / ℃. [5]

[0034] The antenna component as described in any one of [1] to [4], wherein the thermoplastic resin composition comprises (Ab) crystalline resin. [6]

[0036] The antenna component as described in any one of [1] to [5], wherein the thermoplastic resin composition comprises more than 10% by mass of (B) inorganic filler. [7]

[0038] The antenna component as described in any one of [1] to [6], wherein the thermoplastic resin composition comprises more than 10% by mass of (Aa) polyphenylene ether resin. [8]

[0040] The antenna component described in any one of [1] to [7] is used in an outdoor or indoor antenna base station. [9]

[0042] The antenna component, as described in any one of [1] to [8], has a metal coating formed by electroless copper plating process of chromic acid etching.

[10]

[0044] The antenna component as described in any one of [1] to [9], wherein after the metal coating is formed by electroless copper plating by chromic acid etching, the metal layer does not develop cracks after being placed at 85°C and 85% humidity for 2000 hours.

[11]

[0046] The antenna component as described in any one of [1] to

[10] , wherein the thermoplastic resin composition comprises (Aca) polystyrene resin.

[12]

[0048] The antenna component as described in any one of [1] to

[11] , wherein the thermoplastic resin composition comprises (Acb) a block copolymer comprising at least one block of aromatic vinyl monomer unit and at least one block of conjugated diene monomer unit and / or a hydrogenation of the block copolymer.

[13]

[0050] The antenna component as described in any one of [1] to

[12] is an antenna filter.

[14]

[0052] The antenna component as described in any one of [1] to

[12] is an antenna element.

[0053] The effects of the invention

[0054] According to the present invention, an antenna component can be obtained that maintains tightness with the metal coating, while exhibiting small dimensional changes and dielectric loss tangent changes in the high-temperature region, can be formed by injection molding, and is applicable in all environments such as low temperature, high temperature, and humidity. Attached Figure Description

[0055] Figure 1 This is a diagram illustrating the method of cutting test pieces from an ISO dumbbell-shaped specimen for determining the expansion rate in an embodiment. Detailed Implementation

[0056] The present invention will now be described in detail.

[0057] The antenna component of this embodiment has an injection-molded body made of a thermoplastic resin composition. At least a portion of the injection-molded body is metal-coated for use. The thermoplastic resin composition includes (Aa) polyphenylene ether resin. The flexural temperature (DTUL) of the thermoplastic resin composition is 120°C or higher. The temperature of the thermoplastic resin composition when the temperature is increased from -30°C to 120°C is divided into temperature regions with intervals of 10°C. When the lower temperature side of two adjacent temperature regions is designated as the low temperature region and the higher temperature side is designated as the high temperature region, in any two adjacent temperature regions, the expansion rate (mm / mm / °C) of the resin composition in the TD direction in the low temperature region, measured using the method described in ISO 11359, and the expansion rate (mm / mm / °C) of the resin composition in the TD direction in the high temperature region, measured using the method described in ISO 11359, both satisfy the following relationship.

[0058] -50≦((expansion rate of high temperature region - expansion rate of low temperature region) / expansion rate of low temperature region)×100≦50

[0059] The components of the thermoplastic resin composition in this embodiment will be described in detail below.

[0060] [(A) Thermoplastic resin]

[0061] In this embodiment, (A) thermoplastic resin refers to resin components other than fillers, inorganic fillers, etc. Examples of such resin components include various resins used for molding purposes, such as polyphenylene ether resins, polyester resins, polyamide resins, polycarbonate resins, vinyl resins, olefin resins, acrylic resins, aromatic resins, etc.

[0062] The thermoplastic resin (A) of this embodiment, by including (Aa) polyphenylene ether resin, can improve the adhesion to the metal coating and the temperature dependence of the dielectric loss tangent.

[0063] In the thermoplastic resin of this embodiment (A), resin components mainly used to improve impact resistance, such as olefin-based thermoplastic elastomers and hydrogenated block copolymers, may also be included.

[0064] In addition, the thermoplastic resin (A) in this embodiment may simultaneously include crystalline resin (Ab) and other thermoplastic resins, such as polyester resins, polyamide resins, polycarbonate resins, vinyl resins, olefin resins, acrylic resins, aromatic resins, etc.

[0065] From the perspective of low dielectric loss tangent, olefin-based resins are suitable for use, and resins with sufficient heat resistance are preferred. Examples include polyester resins such as polyethylene naphthalate (PEN), polyethylene terephthalate (PET), and polybutylene terephthalate (PBT); and polyolefin polymers such as cyclic olefin polymers (COP), cyclic olefin copolymers, and methylpentene polymers (TPX).

[0066] Examples of olefin-based thermoplastic elastomers include polyolefin homopolymers such as polyethylene and polypropylene; and polyolefin copolymers such as ethylene-propylene copolymers, ethylene-butene copolymers, and ethylene-octene copolymers. In particular, examples of polyethylene homopolymers include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE).

[0067] In addition, examples of hydrogenated block copolymers include hydrogenated block copolymers obtained by hydrogenating a block copolymer composed of polystyrene blocks and conjugated diene polymer blocks.

[0068] There are no particular limitations on the structure of block copolymers before hydrogenation. For example, when polystyrene block chains are represented as S and conjugated diene polymer block chains are represented as B, structures such as SBS, SB-SB, (SB-)4-S, and SBSBS can be given.

[0069] [(Aa) Polyphenylene ether resin]

[0070] Specific examples of the (Aa) polyphenylene ether resin (hereinafter sometimes simply referred to as "(Aa) component") in this embodiment include, for example, 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), etc. Furthermore, examples include polyphenylene ether copolymers such as copolymers of 2,6-dimethylphenol with other phenols (e.g., copolymers with 2,3,6-trimethylphenol and copolymers with 2-methyl-6-butylphenol as described in Japanese Patent Publication No. 52-17880).

[0071] Among these, the polyphenylene ethers that are particularly preferred are copolymers of poly(2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,6-trimethylphenol, or mixtures thereof.

[0072] Examples of the above-mentioned (Aa) component include homopolymers composed of repeating unit structures represented by formula (1) and copolymers having repeating unit structures represented by formula (1).

[0073] The above-mentioned (Aa) component can be used alone or in combination of two or more.

[0074] [Chemistry 1]

[0075]

[0076] In the above formula (1), R 1 R 2 R 3 and R 4 Each of the following is a monovalent group selected independently from the group consisting of hydrogen atom, halogen atom, primary alkyl group having 1 to 7 carbon atoms, secondary alkyl group having 1 to 7 carbon atoms, phenyl group, haloalkyl group, aminoalkyl group, alkyloxy group, and haloalkyloxy group having at least two carbon atoms separating the halogen atom from the oxygen atom.

[0077] Regarding the manufacturing method of (Aa) polyphenylene ether resin, there is no particular limitation as long as it is obtained by a known method. For example, the manufacturing method described in U.S. Patent No. 3,306,874, U.S. Patent No. 3,306,875, U.S. Patent No. 3,257,357 and U.S. Patent No. 3,257,358, Japanese Patent Application Publication Nos. 50-51197, 52-17880 and 63-152628 can be cited.

[0078] The preferred range for the specific viscosity (measured using an Ubbelohde viscometer in 0.5 g / dL chloroform solution at 30°C) of the (Aa) polyphenylene ether resin in this embodiment is 0.30–0.80 dL / g, more preferably 0.35–0.75 dL / g, and most preferably 0.38–0.55 dL / g. When the specific viscosity of the (Aa) polyphenylene ether resin is within this range, it exhibits excellent impact resistance, heat resistance, and other properties, making it a preferred choice.

[0079] In the (Aa) polyphenylene ether resin of this embodiment, a blend made by blending two or more polyphenylene ethers with different specific viscosities can also be preferably used.

[0080] In addition, various known stabilizers can be appropriately used for the stabilization of (Aa) polyphenylene ether resin. Examples of stabilizers include metal stabilizers such as zinc oxide and zinc sulfide, hindered phenolic stabilizers, phosphorus stabilizers, hindered amine stabilizers, and other organic stabilizers. The preferred mixing amount of these stabilizers is less than 5 parts by weight relative to 100 parts by weight of (Aa) polyphenylene ether resin.

[0081] In addition, known additives that can be added to (Aa) polyphenylene ether resins can also be added in an amount of less than 10 parts by weight relative to 100 parts by weight of (Aa) polyphenylene ether resin.

[0082] The aforementioned (Aa) component can be a modified polyphenylene ether obtained by reacting the aforementioned homopolymer and / or copolymer with a styrene monomer or its derivative and / or an α,β-unsaturated carboxylic acid or its derivative. Here, the grafting or addition amount of the aforementioned styrene monomer or its derivative and / or an α,β-unsaturated carboxylic acid or its derivative is preferably 0.01 to 10% by mass relative to 100% by mass of the (Aa) component.

[0083] Examples of methods for manufacturing the aforementioned modified polyphenylene ether include reacting the ether in the presence or absence of a free radical initiator at a temperature of 80–350°C in a molten, solution, or slurry state.

[0084] As the polyphenylene ether described above, a mixture of the above homopolymer and / or the above copolymer with the above modified PPE in any proportion can be used.

[0085] Without including the (Ab) crystalline resin described later, from the perspective of controlling the dielectric constant while ensuring heat resistance and a low dielectric loss tangent, the content of the (Aa) polyphenylene ether resin is preferably 50% by mass or more, preferably 55% by mass or more, and more preferably 60% by mass or more, relative to 100% by mass of the (A) thermoplastic resin. Furthermore, from the perspective of moldability, it is preferably 85% by mass or less.

[0086] Furthermore, in the case of including the (Ab) crystalline resin described later, from the perspective of being able to control the dielectric constant while ensuring heat resistance and a low dielectric loss tangent, the content of the (Aa) polyphenylene ether resin is preferably 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more, relative to 100% by mass of the (A) thermoplastic resin described above. Furthermore, from the perspective of flowability, it is preferably 90% by mass or less.

[0087] In particular, from the perspective of ensuring a low dielectric loss tangent in high-temperature regions, when the total amount of (Aa) polyphenylene ether resin and (Ab) crystalline resin is set to 100 parts by mass, the (Aa) polyphenylene ether resin 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 perspective of flowability, it is preferably 90 parts by mass or less.

[0088] [(Ab) Crystalline Resin]

[0089] This embodiment may include (Ab) crystalline resins. (Aba) polyamide, (Abb) polypropylene, and (Abc) polyphenylene sulfide resins may be used appropriately. In addition, crystalline resins such as polyethylene, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyetheretherketone, liquid crystal polymers, and polytetrafluoroethylene may also be used.

[0090] When the thermoplastic resin composition is set to 100% by mass, the preferred contents of each (Ab) crystalline resin are 90% by mass or less, more preferably 80% by mass or less, and even more preferably 85% by mass or less.

[0091] In particular, from the perspective of ensuring a low dielectric loss tangent in high-temperature regions, when the total amount of (Aa) polyphenylene ether resin and (Ab) crystalline resin is set to 100% by mass, the amount of (Ab) crystalline resin is 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0092] [(Aba) Polyamide]

[0093] The (Aba) polyamide (hereinafter sometimes simply referred to as "(Aba) component") in this embodiment is not particularly limited as long as it has amide bonds {-NH-C(=O)-} in the repeating units of the polymer backbone.

[0094] Generally, polyamides are obtained through ring-opening polymerization of lactams, condensation polymerization of diamines and dicarboxylic acids, condensation polymerization of ω-aminocarboxylic acids, etc., but are not limited to resins obtained by these methods.

[0095] As lactams, examples include ε-caprolactam, heptanolactam, and ω-laurolactam.

[0096] Examples of diamines include aliphatic, alicyclic, and aromatic diamines. Specific examples include tetramethylenediamine, hexamethylenediamine, undecylmethylenediamine, dodecamethylenediamine, tridecylmethylenediamine, 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-diamine. Aliphatic diamines such as octyldiamine, 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, 5-methyl-1,9-nonanediamine, 1,3-diaminomethylcyclohexane, 1,4-diaminomethylcyclohexane, m-phenylenediamine, p-phenylenediamine, m-phenylenediamine, and p-phenylenediamine.

[0097] Dicarboxylic acids can be broadly categorized into aliphatic, alicyclic, and aromatic dicarboxylic acids. Specific examples of dicarboxylic acids include adipic acid, octanoic acid, azelaic acid, sebacic acid, dodecanoic acid, 1,1,3-tridecanoic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and dimer acids.

[0098] In addition, examples of aminocarboxylic acids include ε-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-aminotridecanoic acid.

[0099] In this embodiment, the copolyamides obtained by polycondensing these lactams, diamines, dicarboxylic acids, and ω-aminocarboxylic acids individually or by polycondensing a mixture of two or more of them can be used.

[0100] In addition, substances obtained by polymerizing these lactams, diamines, dicarboxylic acids, and ω-aminocarboxylic acids to low molecular weight oligomers in a polymerization reactor and then increasing their molecular weight using an extruder or similar means can also be used appropriately.

[0101] Examples of (Aba) polyamides that are particularly suitable for use in this 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-phenylenediamine),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, polyamide 6,6 / 12 / 6,I, etc.

[0102] Among these, polyamides copolymerized from multiple polyamides using an extruder or the like can also be used. Preferred polyamides are those selected from polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, and polyamide 12, which are aliphatic polyamides; and polyamide 9,T, polyamide 6 / 6,T, polyamide 6,6 / 6,T, polyamide 6,6 / 6,I, and polyamide MXD,6, which are semi-aromatic polyamides. More preferably, polyamides selected from polyamide 6,6, polyamide 6, polyamide 9,T, and polyamide 6,6 / 6,I are preferred.

[0103] The (Aba) polyamide of this embodiment comprises: a dicarboxylic acid unit (a) containing 60 to 100 mol% of terephthalic acid units, and a diamine unit (b) containing 60 to 100 mol% of aliphatic diamine units having 9 to 12 carbon atoms. It is preferred from the viewpoints of water absorption and heat resistance.

[0104] [[Dicarboxylic acid unit (a)]]

[0105] Regarding the dicarboxylic acid unit (a) in this embodiment, this unit (a) contains 60 to 100 mol% (preferably 70 to 100 mol%, more preferably 80 to 100 mol%, further preferably 90 to 100 mol%, and even more preferably 100 mol%) of terephthalic acid units. By keeping this molar ratio within this range, a resin composition with excellent heat resistance can be prepared. Furthermore, it tends to exhibit excellent recyclability when molding complex shapes or large molded articles.

[0106] The dicarboxylic acid unit (a) may also contain dicarboxylic acid units other than terephthalic acid units. Examples of dicarboxylic acid units include, but are not limited to, units derived from the following substances: aliphatic dicarboxylic acids such as malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyl adipic acid, trimethyl adipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, and octanoic 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, biphenylcarboxylic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, and 4,4'-biphenylcarboxylic acid.

[0107] These units can be a single type or a combination of two or more types.

[0108] The dicarboxylic acid unit other than the terephthalic acid unit mentioned above may be included in the dicarboxylic acid unit (a) in the range of 40 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, more preferably 10 mol% or less, and most preferably 0 mol%.

[0109] [[Diamine unit (b)]]

[0110] 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 even more preferably 100 mol%) of aliphatic diamine units with 9 to 12 carbon atoms. By keeping the number of carbon atoms and the molar ratio of the diamine units within the above range, a resin composition with an excellent balance between low water absorption and heat resistance can be prepared.

[0111] The diamine unit (b) can be either straight-chain or branched.

[0112] Examples of linear aliphatic diamines constituting the diamine unit (b) mentioned above include, but are not limited to, 1,9-nonanediamine (also known as nonamethylenediamine), decamethylenediamine, undecamethylenediamine, and dodecamethylenediamine.

[0113] Examples of aliphatic diamines constituting the diamine unit (b) described above, which are aliphatic diamine units having substituents branching from the main chain, include, but are not limited to, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyl-1,8-octanediamine (also known as 2-methyloctamethylenediamine), and 2,4-dimethyloctamethylenediamine.

[0114] As the diamine unit (b) mentioned above, from the perspective of balancing mechanical strength, low water absorption, and heat resistance, it is preferable to include a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit. Preferably, the 1,9-nonanediamine unit and the 2-methyl-1,8-octanediamine unit are used together.

[0115] As the diamine unit (b) mentioned above, the molar ratio (1,9-nonanediamine unit / 2-methyl-1,8-octanediamine unit) of the 1,9-nonanediamine unit to the 2-methyl-1,8-octanediamine unit is preferably in the range of 100 / 0 to 20 / 80 when the diamine unit includes 1,9-nonanediamine unit and / or 2-methyl-1,8-octanediamine unit. This molar ratio is more preferably 95 / 5 to 60 / 40, and even more preferably 90 / 10 to 75 / 25. When the molar ratio is within this range, there is a tendency to produce resin compositions with particularly excellent heat resistance.

[0116] The diamine unit (b) may also contain a diamine unit other than an aliphatic diamine unit having 9 to 12 carbon atoms. Examples of such a diamine unit include, but are not limited to, units derived from the following substances: aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and 2-methylpentamethylenediamine (also known as 2-methyl-1,5-diaminopentane); alicyclic diamines such as 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclopentanediamine; and aromatic diamines such as m-phenylenediamine.

[0117] These units can be a single type or a combination of two or more types.

[0118] The diamine unit other than the aliphatic diamine unit with 9 to 12 carbon atoms can be included in the dicarboxylic acid unit (ba) in the range of 40 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, more preferably 10 mol% or less, and most preferably 0 mol%.

[0119] Preferred examples of (Aba) polyamides in this embodiment include polyamides 9,T, 10,T, etc.

[0120] In addition, the (Aba) polyamide of this embodiment may include lactam units such as butyrolactam, neopentyl lactam, ε-caprolactam, octyl lactam, heptanolactam, and undecyl lactam, aminocarboxylic acid units such as 6-aminohexanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, polyamine units of 3 or more such as dihexamethylenetriamine, and polycarboxylic acid units of 3 or more such as trimellitic acid, pyromellitic acid, and benzopyrene.

[0121] These units can be a single type or a combination of two or more types.

[0122] The total percentage (mol%) of these units in the (Aba) polyamide is preferably 20 mol% or less, more preferably 10 mol% or less, and even more preferably 5 mol% or less, relative to the total polyamide.

[0123] [Content of (Aba) polyamide]

[0124] In the thermoplastic resin composition of this embodiment, when (A) thermoplastic resin is set to 100% by mass, the content of component (Aba) is preferably 25-75% by mass, more preferably 30-75% by mass, and even more preferably 30-70% by mass. When the content of component (Aba) is within this range, a resin with excellent mechanical strength, low water absorption, dimensional accuracy, and weld strength can be obtained.

[0125] Furthermore, in the thermoplastic resin composition of this embodiment, when the total amount of component (Aa) and component (Aba) is set to 100 parts by mass, the content of component (Aba) 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 (Aba) is within this range, a thermoplastic resin composition with excellent mechanical strength, low water absorption, dimensional accuracy, and weld strength can be produced, and it can be repeatedly molded.

[0126] [(Aba) Polyamide Manufacturing Method]

[0127] There is no particular limitation on the manufacturing method of (Aba) polyamide, and various methods can be cited as examples.

[0128] 1) A method of polymerizing an aqueous solution or suspension of dicarboxylic acid and diamine, or a mixture of dicarboxylic acid and diamine salts with other components such as lactams and / or aminocarboxylic acids (hereinafter sometimes referred to as "the mixture thereof") by heating the aqueous solution or suspension while maintaining the molten state (hereinafter also referred to as "thermal melt polymerization").

[0129] 2) A method of removing the precipitated prepolymer by heating an aqueous solution or aqueous suspension of dicarboxylic acid and diamine or a mixture thereof (“prepolymer method”);

[0130] 3) A method for increasing the degree of polymerization of polyamide obtained by hot melt polymerization at a temperature below its melting point while maintaining a solid state (“hot melt polymerization-solid phase polymerization”);

[0131] 4) A method of increasing the degree of polymerization by heating an aqueous solution or aqueous suspension of dicarboxylic acid and diamine or a mixture thereof, and then remelting the precipitated prepolymer using an extruder such as a kneader (“prepolymer-extrusion polymerization”);

[0132] 5) A method of increasing the degree of polymerization by heating an aqueous solution or aqueous suspension of dicarboxylic acid and diamine or a mixture thereof, thereby maintaining the precipitated prepolymer in a solid state at a temperature below the melting point of the polyamide (“prepolymer-solid phase polymerization”).

[0133] 6) A method for polymerizing dicarboxylic acids and diamines or mixtures thereof while maintaining them in a solid state (“monomer-solid phase polymerization”);

[0134] 7) A method for polymerizing "salts of dicarboxylic acids and diamines" or mixtures thereof while maintaining them in a solid state ("salt-solid phase polymerization");

[0135] 8) A method of polymerization using dicarboxylic acid acyl halides and diamines that are equivalent to dicarboxylic acids (“solution method”).

[0136] Examples of polymerization methods for manufacturing (Aba) polyamides include, but are not limited to, batch and continuous processes.

[0137] There are no particular limitations on the polymerization apparatus, and well-known apparatuses (such as autoclave reactors, drum mixer reactors, extruder reactors, kneaders, etc.) can also be used.

[0138] [Properties of (Aba) polyamide]

[0139] The terminal groups of the (Aba) polyamide contained in the thermoplastic resin composition of this embodiment participate in the reaction with the (Aa) polyphenylene ether resin. Typically, polyamide resins contain amino or carboxyl groups as terminal groups. Generally, an increase in the concentration of terminal carboxyl groups tends to decrease impact resistance and increase flowability. Conversely, an increase in the concentration of terminal amino groups generally tends to increase impact resistance and decrease flowability. However, the physical properties of the thermoplastic resin composition of this embodiment are not limited to these tendencies.

[0140] The concentration of the terminal amino group of component (Aba) is preferably 1 to 80 μmol / g, more preferably 5 to 60 μmol / g, further preferably 10 to less than 45 μmol / g, and even more preferably 20 to 40 μmol / g. By maintaining the terminal amino group concentration within the above range, the balance between the flowability and impact resistance of the thermoplastic resin composition of this embodiment can be maintained to a higher level.

[0141] The concentration of the terminal carboxyl group of component (Aba) is preferably 20 to 150 μmol / g, more preferably 30 to 130 μmol / g. By maintaining the terminal carboxyl group concentration within the above range, the balance between the flowability and impact resistance of the thermoplastic resin composition of this embodiment can be maintained to a higher level.

[0142] The concentration of each terminal group in these polyamides can be adjusted using known methods. For example, one or more methods selected from diamine compounds, monoamine compounds, dicarboxylic acid compounds, and monocarboxylic acid compounds can be added in a manner that achieves a predetermined concentration of terminal groups during the polymerization of the polyamide.

[0143] The concentrations of terminal amino groups and terminal carboxyl groups can be determined by various methods. For example, from the perspectives of accuracy and simplicity, it is preferable to use... 1 H-NMR is a method that determines the concentration of terminal groups based on the integral value of the characteristic signal corresponding to each terminal group. For example, as a specific example of a method for quantitatively determining the concentration of terminal groups in polyamide resins, the method described in the examples of Japanese Patent Application Publication No. 07-228689 can be cited. Specifically, from the perspectives of accuracy and simplicity, the method utilizes… 1 ¹H-NMR (500 MHz, measured in deuterated trifluoroacetic acid at 50 °C) determines the number of terminal groups based on the integral value of the characteristic signal corresponding to each terminal group. In cases where the characteristic signal of the end-capped group cannot be identified, the intrinsic viscosity [η] of the polyamide can be measured, and the total number of terminal groups in the molecular chain can be calculated using the following formula.

[0144] Mn = 21900[η] - 7900 (Mn represents the number-average molecular weight)

[0145] molecular chain terminal groups

[0146] Total (eq / g) = 2 / Mn

[0147] In (Aba) polyamide, it is preferable to end-cap 10% to 95% of the terminal groups of the molecular chain using an end-capping agent. The lower limit of the proportion of terminal groups of the polyamide molecular chain that are end-capped (end-capping rate) is more preferably 40% or more, and even more preferably 60% or more. By ensuring the end-capping rate is above the aforementioned lower limit, the viscosity increase during molding of the thermoplastic resin composition of this embodiment can be suppressed. Furthermore, the upper limit of the end-capping rate is preferably 95% or less, and more preferably 90% or less. By ensuring the end-capping rate is below the aforementioned upper limit, impact resistance and the surface appearance of the molded article can be further improved.

[0148] Regarding the end-capping rate of polyamide, the number of terminal carboxyl groups, terminal amino groups, and terminal groups capped by the end-capping agent in the polyamide can be determined by measuring them separately, and calculated according to the following formula (1).

[0149] End capping rate (%) = [(α-β) / α]×100(1)

[0150] (In the formula, α represents the total number of terminal groups of the molecular chain (unit = moles; it is usually equal to twice the number of polyamide molecules), and β represents the total number of uncapped carboxyl and amino terminals (unit = moles).)

[0151] As a capping agent, there are no particular limitations on monofunctional compounds that are reactive with the amino or carboxyl groups at the end of the polyamide. From the perspectives of reactivity and stability of the capping end, monocarboxylic acids and monoamines are preferred, and from the perspectives of ease of processing, monocarboxylic acids are more preferred. In addition, acid anhydrides, monoisocyanates, monoacyl halides, monoesters, and monoalcohols can also be used as capping agents.

[0152] As for monocarboxylic acids used as end-capping agents, there are no particular limitations as long as they are reactive with amino groups. Examples include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, octanoic acid, lauric acid, tridecanic acid, tetradecanoic acid, palmitic acid, stearic acid, pteropenic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, methylbenzoic acid, α-naphthoic acid, β-naphthoic acid, methylnaphthoic acid, and phenylacetic acid; and any mixtures thereof. Among these, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, octanoic acid, lauric acid, tridecanic acid, tetradecanoic acid, palmitic acid, stearic acid, and benzoic acid are preferred from the perspectives of reactivity, end-capping stability, and economy. Acetic acid and benzoic acid are more preferred.

[0153] As for the monoamines used as end-capping agents, there are no particular limitations as long as they are reactive with carboxyl groups. Examples 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, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferred from the perspectives of reactivity, boiling point, end-capping stability, and economy, and butylamine, hexylamine, and octylamine are more preferred.

[0154] To further improve the heat resistance stability of thermoplastic resin compositions, the resin composition may contain not only polyamides but also transition metals and halogens.

[0155] There are no particular limitations on the types of transition metals; examples include iron, copper, cerium, nickel, and cobalt. Among these, copper is preferred due to its long-term thermal stability. Furthermore, there are no particular limitations on the types of halogens; bromine and iodine are preferred to prevent corrosion of production equipment.

[0156] When the total of components (Aa) and (Aba) in this embodiment is set to 100 parts by mass, the content of transition metals, based on a mass basis, is preferably 1 ppm or more and less than 200 ppm, more preferably 5 ppm or more and less than 100 ppm. Furthermore, when the total of components (Aa) and (Aba) in this embodiment is set to 100 parts by mass, the content of halogens, based on a mass basis, is preferably 500 ppm or more and less than 1500 ppm, more preferably 700 ppm or more and less than 1200 ppm.

[0157] There is no particular limitation on the method for adding these transition metals and halogens to the resin composition. Examples include: adding them in powder form during the melt blending process of polyamide and (Aa); adding them during the polymerization of polyamide; and adding the polyamide masterbatch, which contains a high concentration of transition metals and halogens, to the resin composition after such masterbatch has been manufactured. Preferred methods among these are: adding them during the polymerization of polyamide; and adding them after manufacturing a masterbatch containing a high concentration of transition metals and / or halogens in polyamide.

[0158] In addition, in this embodiment, known organic stabilizers can also be used without problems, in addition to the transition metals and / or halogens mentioned above.

[0159] Examples of organic stabilizers include hindered phenolic 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, and hindered amine-based light stabilizers. Among these organic stabilizers, hindered phenolic antioxidants, phosphorus-based processing heat stabilizers, or combinations thereof are more preferred.

[0160] The preferred mixing amount of these organic stabilizers is 0.001 to 1 part by weight relative to 100 parts by weight of (Aba) polyamide.

[0161] [(Abb) Polypropylene Resins]

[0162] There are no particular limitations on (Abb) polypropylene resins, for example, homopolymers and / or copolymers with propylene as the repeating unit structure, with preferred options being crystalline propylene homopolymers, crystalline propylene-ethylene block copolymers, and mixtures of crystalline propylene homopolymers and crystalline propylene-ethylene block copolymers.

[0163] There are no particular limitations on what constitutes a crystalline propylene-ethylene block copolymer; for example, substances having both a crystalline propylene homopolymer portion and a propylene-ethylene random copolymer portion can be cited.

[0164] From the perspective of suppressing dripping during combustion and improving the balance between fluidity and mechanical strength in the resin composition, the melt mass flow rate (hereinafter also referred to as "MFR") of the (Abb) component is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more, particularly preferably 0.5 g / 10 min or more, and preferably 15 g / 10 min or less, more preferably 6 g / 10 min or less, and particularly preferably 3 g / 10 min or less.

[0165] It should be noted that the MFR can be determined according to ISO 1133 at a temperature of 230°C and a load of 2.16 kg. Specifically, the MFR can be determined by the method described in the examples below.

[0166] There are no particular limitations on the manufacturing method of the (Abb) component; known methods can be used. Specific examples of polypropylene manufacturing methods include methods that polymerize propylene at temperatures of 0–100°C and pressures of 3–100 atmospheres in the presence of a polymerization catalyst composition comprising a titanium trichloride catalyst or a titanium halide catalyst supported on a magnesium chloride support, and an alkyl aluminum compound. In the above methods, chain transfer agents such as hydrogen can be added to adjust the molecular weight of the polymer.

[0167] Furthermore, in the above method, in addition to the aforementioned polymerization catalyst composition, to improve the isotactic regularity of the obtained polypropylene and the polymerization activity of the polymerization system, an electron-donating compound may be further included as an internal or external donor component. There are no particular limitations on these electron-donating compounds, and known substances can be used. Specific examples of electron-donating compounds include ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate, and methyl methyl benzoate; phosphites such as triphenyl phosphite and tributyl phosphite; phosphoric acid derivatives such as hexamethylphosphoryltriamine; alkoxy ester compounds; aromatic monocarboxylic acid esters; aromatic alkyl alkoxysilanes; aliphatic hydrocarbon alkoxysilanes; various ether compounds; various alcohols; and various phenols.

[0168] The polymerization method described above can be either batch polymerization or continuous polymerization. The polymerization method can be solution polymerization and slurry polymerization using solvents such as butane, pentane, hexane, heptane, and octane; as well as bulk polymerization in monomers under solvent-free conditions and gas-phase polymerization in gaseous polymers.

[0169] In the manufacturing method of the (Abb) component, particularly in the manufacturing method of the crystalline propylene-ethylene block copolymer, there is no particular limitation. For example, a method including the following steps can be cited: a first step of obtaining a crystalline propylene homopolymer portion; and a second step of obtaining a propylene-ethylene block copolymer portion formed by copolymerizing the crystalline propylene homopolymer portion with ethylene and other α-olefins added as needed. Here, other α-olefins are not particularly limited, and examples include propylene, 1-butene, and 1-hexene.

[0170] The aforementioned polypropylene resin can be a known modified (grafted or added 0.01 to 10% by weight of the α,β-unsaturated carboxylic acid or its derivative) polyolefin resin obtained by reacting a polyolefin resin with an α,β-unsaturated carboxylic acid or its derivative in the presence or absence of a free radical initiator in a molten state or a solution state at a temperature of 30 to 350°C. Alternatively, it can be a mixture of the aforementioned polypropylene resin and the modified polyolefin resin in any proportion.

[0171] One reason for using modified polyolefin resins is the improved interfacial adhesion between the resin and the filler. By adding modified polyolefins, the improved interfacial adhesion between the resin and the filler increases strength.

[0172] [Ratio of (Aa) polyphenylene ether resin to (Abb) polypropylene]

[0173] In this embodiment, regarding the preferred content ratio of components (Aa) and (Abb), when the total amount of components (Aa) and (Abb) is set to 100 parts by mass, the content of component (Aa) is 10 to 70 parts by mass and the content of component (Abb) is 30 to 90 parts by mass. More preferably, the content of component (Aa) is 10 to 60 parts by mass and the content of component (Abb) is 40 to 90 parts by mass. Even more preferably, the content of component (Aa) is in the range of 10 to 50 parts by mass and the content of component (Abb) is 50 to 90 parts by mass. When the content ratio of component (Aa) to component (Abb) is within this range, the balance of impact resistance, heat resistance, and tensile strength is excellent, which is preferred.

[0174] It should be noted that these proportions in the resin composition can be determined using Fourier transform infrared spectroscopy (FT-IR) via the calibration curve method.

[0175] [(Abc) polyphenylene sulfide resin]

[0176] The polyphenylene sulfide resin (Abc) used in this embodiment is divided into two types according to its manufacturing method: linear polyphenylene sulfide resin (hereinafter sometimes simply referred to as linear PPS) and cross-linked polyphenylene sulfide resin (hereinafter sometimes simply referred to as cross-linked PPS).

[0177] [[Linear PPS]]

[0178] The former linear PPS is a polymer containing repeating units of the following chemical formula (1), typically 50 mol% or more, preferably 70 mol% or more, and more preferably 90 mol% or more.

[0179] [-Ar-S-]···(1)

[0180] (Here, Ar represents arylene. Examples of arylene groups include p-phenylene, m-phenylene, substituted phenylene (preferably alkyl or phenyl groups with 1 to 10 carbon atoms), p,p'-diphenylenesulfonyl, p,p'-biphenylene, p,p'-diphenylenecarbonyl, naphthylene, etc.)

[0181] Linear PPS can be a homopolymer with arylene groups as the structural unit, or, from the perspective of processability and heat resistance, a copolymer obtained by mixing two or more different arylene groups. Among them, linear PPS with repeating units of p-phenylene sulfide as the main constituent element has excellent processability and heat resistance, and is readily available industrially, and is therefore preferred.

[0182] The preferred methods for manufacturing this linear PPS are generally: polymerization of a halogen-substituted aromatic compound, such as p-dichlorobenzene, in the presence of sulfur and sodium carbonate; polymerization in a polar solvent in the presence of sodium sulfide or sodium hydrosulfide and sodium hydroxide, or in the presence of hydrogen sulfide and sodium hydroxide or sodium aminoalkanoate; self-condensation of p-chlorobenzene thiophenol, etc., wherein 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.

[0183] These manufacturing methods are well known, and linear PPS can be obtained, for example, by methods described in U.S. Patent No. 2,513,188, Japanese Patent Publication Nos. 44-27671, 45-3368, 52-12240, 61-225217, U.S. Patent No. 3,274,165, 46-27255, Belgian Patent No. 29,437, and Japanese Patent Publication No. 5-222196, as well as by prior art methods illustrated in these documents.

[0184] In the preferred linear PPS, the amount of dichloromethane extracted is 0.7% by mass or less, preferably 0.5% by mass or less, and the terminal -SX group (S is a sulfur atom, X is an alkali metal or hydrogen atom) is 20 μmol / g or more, preferably 20 to 60 μmol / g.

[0185] Here, the determination of the amount of dichloromethane extracted can be performed by the following method.

[0186] Add 5g of linear PPS powder to 80mL of dichloromethane and perform Soxhlet extraction for 6 hours. After cooling to room temperature, transfer the extracted dichloromethane solution to a weighing bottle. Then, use a total of 60mL of dichloromethane in three portions to clean the container used in the extraction, and collect the cleaning solution back into the weighing bottle. Next, heat to approximately 80°C to evaporate the dichloromethane in the weighing bottle, weigh the residue, and determine the extraction amount based on dichloromethane, i.e., the proportion of oligomers present in the linear PPS.

[0187] In addition, the quantification of the -SX group can be performed by the following method: Linear PPS powder is pre-dried at 120°C for 4 hours. Then, 20g of the dried linear PPS powder is added to 150g of N-methyl-2-pyrrolidone and vigorously stirred at room temperature for 30 minutes to eliminate powder agglomerates, forming a slurry. This slurry is filtered and washed repeatedly 7 times with 1 liter of warm water at approximately 80°C. The resulting filter cake is then slurried again in 200g of pure water, and the pH of the slurry is adjusted to 4.5 by adding 1N hydrochloric acid.

[0188] Next, the mixture was stirred at 25°C for 30 minutes, filtered, and washed repeatedly 6 times with 1 liter of warm water at approximately 80°C. The resulting filter cake was then slurried again in 200g of pure water, and then titrated with 1N sodium hydroxide. The amount of -SX groups present in the linear PPS could be determined based on the amount of sodium hydroxide consumed.

[0189] Here, as a specific example of a method for manufacturing linear PPS that satisfies the requirement of an extraction amount of 0.7% by mass or less based on dichloromethane and a terminal -SX group of 20 μmol / g or more, the method described in Japanese Patent Application Publication No. 8-253587 can be cited. In this method, an alkali metal sulfide is reacted with a dihaloaromatic compound in an organic amide solvent, and during the reaction, a portion of the gas phase inside the reaction vessel is condensed by cooling the gas phase portion of the reaction vessel and refluxed back to the liquid layer above the reaction solution, thereby reducing the oligomer content.

[0190] Crosslinked PPS

[0191] Furthermore, regarding cross-linked (including semi-cross-linked) polyphenylene sulfide resin, it is produced by further heating the above-mentioned linear PPS in the presence of oxygen at a temperature below the melting point of polyphenylene sulfide resin to promote oxidative cross-linking and moderately increase the molecular weight and viscosity of the polymer.

[0192] In this crosslinked PPS, from the perspectives of reducing gas buildup and preventing sticking during molding of the resin composition obtained in this invention, it is most preferable to have crosslinked PPS with volatile components captured in the molten state at 320°C of less than 1000 ppm by mass. The quantification of volatile components captured in the molten state at 320°C can be performed by the following method.

[0193] Specifically, 0.5 g of cross-linked PPS powder is weighed into a test tube with an inlet and outlet and a seal. The powder is immersed in a solder bath heated to 320°C for 30 minutes. Simultaneously, nitrogen gas is injected through the inlet of the test tube at a flow rate of 100 cc / min. The gas generated in the test tube, including volatile components from cross-linked PPS, is purified through the outlet. The purified gas is then bubbled through the inlet of a sealed test tube containing acetone, allowing the volatile components to dissolve in the acetone. The volatile components of the cross-linked PPS dissolved in the acetone are analyzed using gas chromatography-mass spectrometry (GC-MS) at temperatures ranging from 50°C to 290°C, quantifying the components with the same sensitivity as monochlorobenzene. This allows the determination of the volatile components in the cross-linked PPS.

[0194] To obtain cross-linked PPS with a volatile content of less than 1000 ppm by mass when captured in the molten state at 320°C, measures are typically taken regarding the polymer concentration and solvent composition during the linear PPS polymerization stage, or regarding the cleaning method for recovering the polymer in the post-polymerization stage, to change the temperature and time of the subsequent high-temperature treatment in the cross-linking stage. This allows for the production of cross-linked PPS with the desired volatile content.

[0195] Acid-modified PPS

[0196] Furthermore, PPS can also be obtained by acid modification of these PPS (linear PPS, cross-linked PPS). The acid-modified PPS here refers to the substance obtained by modifying the aforementioned 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; saturated aliphatic carboxylic acids; and aromatic substituted carboxylic acids. Additionally, inorganic acid compounds such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, and carbonic acid can also be used as examples of such acid compounds.

[0197] Melt viscosity of PPS

[0198] The linear PPS and cross-linked PPS mentioned above can be substances with a melt viscosity of 1 to 10,000 Pa·s at 300°C, preferably 50 to 8,000 Pa·s, and more preferably 100 to 5,000 Pa·s.

[0199] In the instruction manual, melt viscosity refers to the value measured using JIS K-7210 as the reference test method, with a flow tester (Shimadzu Corporation CFT-500 model), after preheating PPS at 300°C for 6 minutes, under the conditions of a load of 196N and a die length (L) / die diameter (D) of 10mm / 1mm.

[0200] [(Ac) Amorphous thermoplastic resins other than polyphenylene ether]

[0201] [[(Aca) polystyrene resin]]

[0202] In this embodiment, (A) the matrix resin may include a polystyrene-based resin. Examples of polystyrene-based resins include atactic polystyrene, rubber-reinforced polystyrene (high-impact polystyrene, HIPS), styrene-acrylonitrile copolymer (SAN) with a styrene content of 50% by weight or more, and ABS resin made by rubber reinforcement of the styrene-acrylonitrile copolymer, with atactic polystyrene and / or high-impact polystyrene being preferred.

[0203] The aforementioned polystyrene-based resins can be used alone or in combination of two or more. It should be noted that the polystyrene-based resins mentioned above do not include the (Acd)styrene-glycidyl methacrylate copolymer described later.

[0204] In this embodiment, when the (Aa) polyphenylene ether resin is set to 100 parts by weight, the preferred content of the (Aca) polystyrene resin is 0 to 100 parts by weight, more preferably 0 to 90 parts by weight, and even more preferably 0 to 80 parts by weight.

[0205] [[(Acb) a block copolymer comprising 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 hydride of the block copolymer]]

[0206] In this embodiment, the component may further include (Acb) a block copolymer comprising at least one block primarily composed of an aromatic vinyl monomer unit and at least one block primarily composed of a conjugated diene monomer unit, and / or a hydrogenated form of the block copolymer (hereinafter sometimes simply referred to as the "(Acb) component"), preferably the (Acb) component. In this embodiment, (Acb) comprising at least one block primarily composed of an aromatic vinyl monomer unit and at least one block primarily composed of a conjugated diene monomer unit, and / or a hydrogenated form of the block copolymer, refers to a non-hydrogenated block copolymer comprising at least one aromatic vinyl polymer block primarily composed of an aromatic vinyl monomer unit and at least one conjugated diene polymer block primarily composed of a conjugated diene monomer unit, and / or a hydrogenated form of the block copolymer.

[0207] It should be noted that the phrase "mainly composed of aromatic vinyl monomer units" in the above-mentioned aromatic vinyl polymer blocks refers to blocks in which 50% or more by mass is an aromatic vinyl monomer unit. More preferably, the aromatic vinyl monomer unit content is 70% or more by mass, further preferably 80% or more by mass, and most preferably 90% or more by mass.

[0208] Furthermore, the phrase "mainly composed of conjugated diene monomer units" in the aforementioned conjugated diene polymer blocks also refers to blocks in which 50% by mass or more is composed of conjugated diene monomer units. More preferably, the conjugated diene monomer units are 70% by mass or more, further preferably 80% by mass or more, and most preferably 90% by mass or more.

[0209] Furthermore, the aforementioned aromatic vinyl polymer block can be, for example, a copolymer block formed by randomly combining a small amount of conjugated diene compound into an aromatic vinyl polymer block. Similarly, the aforementioned conjugated diene polymer block can also be, for example, a copolymer block formed by randomly combining a small amount of aromatic vinyl compound into a conjugated diene polymer block.

[0210] There are no particular limitations on the aromatic vinyl compounds used to form aromatic vinyl monomer units. Examples include styrene, α-methylstyrene, vinyltoluene, etc., and one or more compounds selected from them can be used, with styrene being particularly preferred.

[0211] There are no particular limitations on the conjugated diene compounds used to form the conjugated diene polymer blocks. Examples include butadiene, isoprene, isoprene, 1,3-pentadiene, etc. One or more compounds selected from these can be used, with butadiene, isoprene, and combinations thereof being preferred.

[0212] In the microstructure of the conjugated diene polymer block portion of the above-mentioned block copolymer, the content of 1,2-vinyl or the total amount of 1,2-vinyl and 3,4-vinyl (total vinyl bonding) is preferably 5 to 85%, more preferably 10 to 80%.

[0213] It should be noted that the total vinyl bond content can be determined using an infrared spectrophotometer.

[0214] In the manufacture of the hydrogenated block copolymers (hydrogenated block copolymers), the non-hydrogenated block copolymers used are preferably block copolymers in which the aromatic vinyl polymer block (A) and the conjugated diene polymer block (B) have a bonding form selected from AB type, ABA type, and ABAB type. Among these, block copolymers with different bonding forms may also be used in combination. More preferably, they have a bonding form selected from ABA type and ABAB type, and even more preferably, they have an ABA type bonding form.

[0215] Furthermore, the (Acb) component used in this embodiment is preferably a partially hydrogenated block copolymer (partially hydrogenated block copolymer).

[0216] Partially hydrogenated block copolymers refer to non-hydrogenated block copolymers in which the aliphatic double bonds in the conjugated diene polymer blocks are controlled to be greater than 0% and less than 100%. The preferred hydrogenation rate of such partially hydrogenated block copolymers is 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%.

[0217] Furthermore, the number-average molecular weight of the (Acb) component used in this embodiment is preferably 30,000 or more and less than 300,000. When the number-average molecular weight is within this range, a composition with excellent flowability, impact strength, and flame retardancy can be obtained.

[0218] The method for evaluating the number-average molecular weight of the (Acb) component in the resin composition is as follows. Specifically, the (Acb) component is extracted using a solvent (e.g., chloroform) that exhibits good solubility in the (Acb) component and poor solubility in the (Aa) polyphenylene ether resin. The number-average molecular weight is determined using a gel permeation chromatography apparatus [GPC SYSTEM21: manufactured by Showa Denko Corporation] with a UV spectrophotometer [UV-41: manufactured by Showa Denko Corporation], and calculated using standard polystyrene.

[0219] It should be noted that the measurement conditions can be as follows: [solvent: chloroform, temperature: 40℃, column: sample side (KG, K-800RL, K-800R), reference side (K-805L×2 columns), flow rate 10mL / min, measurement wavelength: 254nm, pressure 15~17kg / cm²] 2 )).

[0220] Additionally, when determining the number-average molecular weight, low molecular weight components may be detected due to catalyst deactivation during polymerization. In such cases, these low molecular weight components are not included in the molecular weight calculation. These low molecular weight components refer to those with a molecular weight of 3000 or less. Typically, the correctly calculated molecular weight distribution (weight-average molecular weight / number-average molecular weight) is within the range of 1.0 to 1.1.

[0221] Provided that the spirit of the invention is not violated, among these block copolymers that can be used as (Acb) components in this embodiment, two or more substances may be mixed together, such as substances with different bonding forms, substances with different types of aromatic vinyl compounds, substances with different types of conjugated diene compounds, substances with different contents of 1,2-bonded vinyls or 1,2-bonded vinyls and 3,4-bonded vinyls, substances with different contents of aromatic vinyl compounds, substances with different hydrogenation rates, etc.

[0222] In addition, these block copolymers used as (Acb) components in this embodiment may also be block copolymers that have been modified in whole or in part.

[0223] The modified block copolymers referred to herein are block copolymers modified using at least one modifying compound having at least one carbon-carbon double or triple bond and at least one carboxylic acid group, anhydride group, amino group, hydroxyl group or glycidyl group in its molecular structure.

[0224] As a method for preparing the modified block copolymer, examples include (1) a method of melting and reacting the modified compound with the block copolymer in a temperature range above the softening point temperature of the block copolymer and below 250°C, with or without a free radical initiator; (2) a method of reacting the block copolymer and the modified compound in solution at a temperature below the softening point of the block copolymer; and (3) a method of reacting the block copolymer and the modified compound in a non-melting state at a temperature below the softening point of the block copolymer. Any of these methods may be used, but method (1) is preferred. Furthermore, in method (1), the method in the presence of a free radical initiator is most preferred.

[0225] As referred to herein, “at least one modified compound having at least one carbon-carbon double or triple bond and at least one carboxylic acid group, anhydride group, amino group, hydroxyl group or glycidyl group in its molecular structure”, the same substance as the modified compound described in the modified polyphenylene ether can be used.

[0226] In this embodiment, when the (Aa) polyphenylene ether resin is set to 100 parts by weight, the preferred content of the (Acb) component is 1 to 40 parts by weight, more preferably 2 to 35 parts by weight, and even more preferably 2 to 30 parts by weight.

[0227] In addition, in this embodiment, from the perspective of being able to control the dielectric constant while maintaining a low dielectric loss tangent, the total content of the above-mentioned (A) thermoplastic resin, the above-mentioned (Aa) polyphenylene ether resin and the above-mentioned (Acb) component is preferably 20% by mass or more, preferably 25% by mass or more, and more preferably 30% by mass or more, relative to 100% by mass of the above-mentioned (A) thermoplastic resin.

[0228] [[(Acc) Ethylene-α-olefin copolymer]]

[0229] The thermoplastic resin composition of this embodiment may contain copolymers of ethylene and α-olefins other than ethylene (ethylene-α-olefin copolymers: hereinafter sometimes simply referred to as "(Acc) components").

[0230] Here, from the perspective of the chemical resistance and impact resistance of the obtained resin composition, the monomer units constituting the (Acc) component preferably do not contain propylene units. It should be noted that "not containing propylene units" in "olefin polymer composed of olefins" also includes cases where propylene is included as a structural unit to a degree that does not impair the effect of the invention, for example, meaning that the content of propylene units in all structural units constituting the (Acc) component is less than 0.1% by mass.

[0231] Examples of (Acc) components include copolymers of ethylene with one or more C3- to C20 α-olefins. Copolymers of ethylene with one or more C3- to C8 α-olefins are more preferred, copolymers of ethylene with 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 with 1-butene are particularly preferred. By using this copolymer as the (Acc) component, it is desirable to obtain resin compositions with higher impact resistance and higher chemical resistance.

[0232] Component (Acc) can be used alone or in combination with two or more. In addition, as component (c), two or more ethylene-α-olefin copolymers can be used.

[0233] From the perspective of the flexibility of the resin composition, the content of ethylene in the (Acc) component is preferably 5 to 95% by mass, more preferably 30 to 90% by mass, relative to the total amount of olefin polymers.

[0234] The content of α-olefins other than ethylene in the (Acc) component is not particularly limited. From the perspective of the softness of the resin composition, it is preferably 5% by mass or more, more preferably 20% by mass or more, relative to the total amount of olefin polymers. In addition, from the perspective of the rigidity of the resin composition, it is preferably 50% by mass or less, more preferably 48% by mass or less.

[0235] The embrittlement temperature of the (Acc) component is below -50°C, and from the perspective of obtaining better impact resistance and chemical resistance, it is preferably below -60°C, and more preferably below -70°C.

[0236] It should be noted that the above embrittlement temperature can be determined according to ASTM D746.

[0237] [[(Acd)styrene-glycidyl methacrylate copolymer]]

[0238] The thermoplastic resin composition of this embodiment may contain (Acd) styrene-glycidyl methacrylate copolymer (hereinafter sometimes simply referred to as the "(Acd) component"). The (Acd) component functions as a mixture of (Aa) polyphenylene ether resin and (Abc) polyphenylene sulfide resin.

[0239] The (Acd) component can be any copolymer containing styrene and glycidyl methacrylate as monomers, and may also contain other monomers. Preferably, it is a copolymer with a total content of 65-100% by mass of the styrene-derived structure and the glycidyl methacrylate-derived structure. More preferably, this content is 75-100% by mass, and may also be 100% by mass.

[0240] In addition, the (Acd) component preferably contains 0.3 to 20% by mass of a structure derived from glycidyl methacrylate, more preferably 1 to 15% by mass, and even more preferably 3 to 10% by mass.

[0241] [(B) Inorganic filler]

[0242] In the thermoplastic resin composition of this embodiment, in addition to the above-mentioned components, inorganic fillers may be added at any stage as needed. By adding inorganic fillers, dimensional changes at high temperatures can be suppressed.

[0243] 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, silicon dioxide, calcium carbonate, kaolin, calcined kaolin, wollastonite, diaspore, apatite, glass beads, glass flakes, and titanium dioxide. 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 preferred inorganic fillers. Additionally, inorganic fillers can also be substances that have undergone surface treatment using known methods with surface treatment agents such as silane coupling agents. Since natural mineral-based fillers often contain trace amounts of iron, it is necessary to select materials that have been refined to remove iron.

[0244] When the thermoplastic resin composition is set to 100% by mass, the 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.

[0245] Furthermore, as a preferred content of the inorganic filler as a whole, when the thermoplastic resin composition is set to 100% by mass, it is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more.

[0246] [Coloring agent]

[0247] In this embodiment, there are no particular limitations on the coloring method of the resin composition, and one or more colorants selected from known organic dyes / pigments and inorganic pigments can be used.

[0248] Examples of organic dyes / pigments include azo lake pigments, benzimidazolone pigments, diaryl compound pigments, condensed azo pigments, phthalocyanine blue and phthalocyanine green pigments, isoindolineone pigments, quinolineone pigments, quinacridone pigments, perylene pigments, anthraquinone pigments, violet ketone pigments, dioxazine violet and other fused polycyclic pigments, azazine pigments, and carbon black.

[0249] Among them, the preferred carbon black is dibutyl phthalate (DBP) with an absorption capacity of less than 250 mL / 100 g, more preferably less than 150 mL / 100 g, and a nitrogen adsorption specific surface area of ​​less than 900 m². 2 / g, further preferred to be less than 400m 2 / g. When they are in this range, compositions with particularly excellent colorability, mechanical strength, and flame retardancy can be obtained.

[0250] The DBP absorbance and nitrogen adsorption specific surface area mentioned here refer to the values ​​measured using the methods specified in ASTM D2414 and JIS K6217, respectively.

[0251] Examples of azazon dyes include Solvent Black 5 (CI50415, CAS No. 11099-03-9), Solvent Black 7 (CI50415:1, CAS No. 8005-20-5 / 101357-15-7), and Acid Black 2 (CI50420, CAS No. 8005-03-6 / 68510-98-5) in terms of colorimetric index.

[0252] Examples of inorganic pigments include metal oxides other than iron oxide, such as titanium oxide, zinc oxide, and chromium oxide, as well as composite metal oxides such as titanium yellow, cobalt blue, and ultramarine.

[0253] Regarding the preferred content of the aforementioned colorant, when the total resin composition is set to 100% by mass, the carbon black is 2% by mass or less, the azine-based dye is 2% by mass or less, and the inorganic pigment is 8% by mass or less. More preferably, the carbon black is 1% by mass or less, the azine-based dye is 1% by mass or less, and the inorganic pigment is 5% by mass or less. By adding the above-mentioned amounts, a good balance between impact resistance and mechanical properties can be maintained. Furthermore, in applications requiring flame retardancy, the above-mentioned amounts are preferred from a flame retardancy perspective.

[0254] [(C) Other ingredients]

[0255] In addition to the components described above, the resin composition of this embodiment may also include, 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 represented by hindered phenolic antioxidants, antioxidants, ultraviolet absorbers, light stabilizers, lubricants such as ethylene bis-stearamide, and modifying materials such as maleic anhydride.

[0256] When the resin composition as a whole is set to 100% by mass, (C) the preferred contents of each of the other components are 15% by mass or less, more preferably 13% by mass or less, and even more preferably 10% by mass or less.

[0257] In addition, as a preferred content of the other components in (C), when the resin composition is set to 100% by mass, it is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0258] Properties of Thermoplastic Resin Compositions

[0259] The characteristics of the thermoplastic resin composition of this embodiment will be described below.

[0260] The load flexural temperature (DTUL) (°C) of the thermoplastic resin composition in this embodiment is preferably a higher value, from the perspective of not easily deforming even when the base station heats up with the increase of communication speed. Specifically, DTUL is 120°C or higher, preferably 130°C or higher, and more preferably 140°C or higher.

[0261] It should be noted that the load flexural temperature (DTUL) refers to the value measured using the method described in the examples below.

[0262] When the dielectric loss tangent of the thermoplastic resin composition in this embodiment is smaller, it indicates a lower energy loss rate, which is preferred.

[0263] It should be noted that the dielectric loss tangent refers to the value measured by the method described in the embodiments below.

[0264] Furthermore, from the perspective of maintaining a low dielectric loss tangent even when the base station heats up due to the increase in communication speed, it is preferable that the temperature dependence of the dielectric loss tangent of the thermoplastic resin composition at 28 GHz satisfies the following conditions.

[0265] Condition 1: When the DTUL is above 120℃ and below 140℃, the difference between the dielectric loss tangent at 23℃ and the dielectric loss tangent at 120℃ is less than 0.004.

[0266] Condition 2: When the DTUL is above 140°C, the difference between the dielectric loss tangent at 23°C and the dielectric loss tangent at 140°C is less than 0.004.

[0267] The temperature dependence of the dielectric loss tangent mentioned above tends to be adjusted to the above range by including a thermoplastic resin (e.g., (Aa) polyphenylene ether resin) with a low dielectric loss tangent and a high glass transition temperature in the thermoplastic resin composition.

[0268] In the thermoplastic resin composition used in the antenna component of this embodiment, the temperature of the composition when the temperature is raised from -30°C to 120°C is divided into temperature regions with intervals of 10°C. When the lower temperature side of two adjacent temperature regions is designated as the low temperature region and the higher temperature side as the high temperature region, in any of the two adjacent temperature regions, the expansion rate (mm / mm / °C) of the thermoplastic resin composition in the TD direction in the low temperature region, measured using the method described in ISO 11359, and the expansion rate (mm / mm / °C) of the resin composition in the TD direction in the high temperature region, measured using the method described in ISO 11359, both satisfy the following relationship.

[0269] -50≦((expansion rate of high temperature region - expansion rate of low temperature region) / expansion rate of low temperature region)×100≦50

[0270] Therefore, antenna components formed by injection molding tend to have a metal coating that is less prone to peeling due to temperature changes, and can also suppress deformation of the component itself caused by temperature changes.

[0271] The above relationship is more preferably...

[0272] -45≦((expansion rate of high temperature region-expansion rate of low temperature region) / expansion rate of low temperature region)×100≦45, further preferably

[0273] -40≦((expansion rate of high temperature region - expansion rate of low temperature region) / expansion rate of low temperature region)×100≦40.

[0274] The aforementioned temperature regions refer to the division of the temperature range from -30℃ to 120℃ into 15 temperature zones: -30℃ to -20℃, -20℃ to -10℃, -10℃ to 0℃, ..., and 110℃ to 120℃. Furthermore, two adjacent temperature zones refer to any one of 14 combinations of adjacent temperature zones within these 15 zones.

[0275] The above relationship is satisfied in all combinations (14 combinations) of two adjacent temperature regions selected from the 15 temperature regions.

[0276] It should be noted that the expansion rate of the above resin composition in the TD direction determined by the method described in ISO 11359 refers to the value measured using test pieces prepared by the method described in the following examples under the conditions described in the following examples.

[0277] By including polyphenylene ether, an amorphous thermoplastic resin with a high glass transition temperature, in the thermoplastic resin composition, the variation in the expansion rate in adjacent temperature regions can be reduced, and the relationship of the aforementioned expansion rate can be adjusted.

[0278] From the perspective of suppressing plating peeling, the average value of the expansion rate in the TD direction (the average of 15 expansion rate values, sometimes referred to as the "average expansion rate" in this specification) measured using the method described in ISO 11359, in 15 temperature zones divided at 10°C intervals when the temperature is raised from -30°C to 120°C, is preferably 10 × 10⁻⁶. - 5 Below mm / mm / ℃, more preferably 9×10 -5 Below mm / mm / ℃, further preferably 8×10 -5 Below mm / mm / ℃.

[0279] The above average value can be kept within the above range by using a resin with a low expansion rate and by adjusting the type and amount of inorganic filler.

[0280] In the thermoplastic resin composition of this embodiment, the maximum value of the expansion rate in the TD direction, measured using the method described in ISO 11359, is preferably 10 × 10⁻⁶ in the above-mentioned temperature region, which is divided into 15 temperature zones at 10°C intervals when the temperature is raised from -30°C to 120°C. -5 mm / mm / ℃ or less, more preferably 2×10 -5 mm / mm / ℃~8×10 -5 mm / mm / ℃. The maximum value above is 10×10 -5 When the temperature is below mm / mm / ℃, it can suppress large dimensional changes caused by temperature rise and is less likely to cause peeling of the metal coating.

[0281] The above maximum values ​​can be kept within the above range by using resins with low expansion rates and by adjusting the type and mixing amount of inorganic fillers.

[0282] (Method for manufacturing the resin composition)

[0283] The resin composition of this embodiment can be manufactured by melt-blending the components constituting component (A), as well as colorants, inorganic fillers, and other components if necessary.

[0284] Examples of melt-mixing machines for melt mixing include, but are not limited to, single-screw extruders, multi-screw extruders including twin-screw extruders, heated melt-mixing machines based on rollers, kneaders, Brayburn plasticizers, and Banbury mixers. Twin-screw extruders are particularly preferred from the perspective of mixability. Specifically, examples include the ZSK series manufactured by WERNER & PFLEIDERER, the TEM series manufactured by TOSHIBA MACHINE CO.,LTD, and the TEX series manufactured by Nippon Steel Works Co., Ltd.

[0285] Regarding the melting and mixing temperature at this time, for crystalline resins, a temperature above the melting point of the crystalline resin can be selected for heating and melting to ensure smooth processing. For amorphous resins, a temperature above the glass transition temperature can be selected for heating and melting to ensure smooth processing. Generally, it can be arbitrarily selected from 200 to 370°C.

[0286] The following describes a preferred manufacturing method using an extruder.

[0287] The L / D (effective barrel length / barrel inner diameter) of the extruder is preferably 20 to 60, more preferably 30 to 50.

[0288] There are no particular limitations on the configuration of the extruder. For example, it is preferable to provide a first raw material supply port upstream of the raw material flow direction, a first vacuum exhaust port downstream of the first raw material supply port, a second raw material supply port downstream of the first vacuum exhaust port (if necessary, a third and fourth raw material supply port may be further provided downstream of the second raw material supply port), and a second vacuum exhaust port downstream of the second raw material supply port. More preferably, a kneading section is provided upstream of the first vacuum exhaust port, between the first vacuum exhaust port and the second raw material supply port, and between the second to fourth raw material supply ports and the second vacuum exhaust port.

[0289] There are no particular limitations on the method of supplying raw materials to the second to fourth raw material supply ports. Compared with simply adding raw materials from the open ports of the second to fourth raw material supply ports of the extruder, the method of supplying raw materials from the open ports of the extruder side using a forced side feeder tends to provide more stable supply and is therefore preferred.

[0290] Especially when the raw materials contain powder and it is desirable to reduce the generation of crosslinks or carbides caused by the thermal history of the resin, it is more preferable to use a forced side feeder supplied from the side of the extruder. More preferably, a forced side feeder is provided at the 2nd to 4th raw material supply ports to supply these raw material powders separately.

[0291] In addition, when adding liquid raw materials, it is preferable to use methods such as plunger pumps or gear pumps to add them to the extruder.

[0292] Furthermore, the upper openings of the second to fourth raw material supply ports of the extruder can also be used as openings to release the air being conveyed along with it.

[0293] There are no particular limitations on the melt mixing temperature and screw speed in the melt mixing process of the resin composition. For crystalline resins, a temperature above the melting point of the crystalline resin can be selected for heating and melting to ensure smooth processing. For amorphous resins, a temperature above the glass transition temperature can be selected for heating and melting to ensure smooth processing. Generally, it can be arbitrarily selected from 200 to 370°C, and the screw speed is set to 100 to 1200 rpm.

[0294] As one specific method for preparing the resin composition of this embodiment using a twin-screw extruder, an example method is as follows: Each component constituting component (A) and the raw material titanium dioxide are supplied to the first feed port of the twin-screw extruder; the heating and melting zone is set to the melting temperature of the thermoplastic resin; and melt mixing is performed at a screw speed of 100–1200 rpm, preferably 200–500 rpm. Furthermore, regarding the location for supplying each component constituting component (A) and the raw material titanium dioxide to the twin-screw extruder, they can be supplied together from the first feed port of the extruder as described above, or a second, third, and fourth feed port can be provided to supply each component separately.

[0295] Furthermore, to reduce the formation of crosslinks or carbides in the resin due to thermal history in the presence of oxygen, it is preferable to maintain the oxygen concentration in each process line of the raw material addition path into the extruder at less than 1.0% by volume. The addition path is not particularly limited, but a specific example is a configuration consisting of piping, a weight-type feeder with a replenishment tank, piping, a feed hopper, and a twin-screw extruder, starting from the storage tank. The method for maintaining such a low oxygen concentration is not particularly limited; introducing an inert gas into each process line with improved airtightness is effective. Generally, it is preferable to introduce nitrogen to maintain the oxygen concentration at less than 1.0% by volume.

[0296] Regarding the manufacturing method of the above-mentioned resin composition, when the thermoplastic resin in component (A) includes a powdered component (volume average particle size less than 10 μm), when manufacturing the resin composition of this embodiment using a twin-screw extruder, it will have the effect of further reducing the residue on the screw of the twin-screw extruder, and thus the resin composition obtained by the above-mentioned manufacturing method can have the effect of reducing the generation of black spot foreign matter, carbides, etc.

[0297] As a specific method for manufacturing the resin composition of this embodiment, it is preferable to use an extruder that controls the oxygen concentration at each raw material supply port to be less than 1.0% by volume and to carry out any one of the methods described in 1 to 3 below.

[0298] Manufacturing method 1: The total amount of each component (A) contained in the resin composition constituting this embodiment is melt-blended (first blending step), and the entire amount of raw material titanium dioxide is supplied to the molten blend obtained in the first blending step, and then melt-blended (second blending step).

[0299] Manufacturing method 2: The total amount of each component (A) contained in the resin composition constituting this embodiment and a portion of the raw material titanium dioxide are melt-blended (first blending step), and the remaining amount of raw material titanium dioxide is supplied to the molten blend obtained in the first blending step, and then melt-blended (second blending step).

[0300] Manufacturing method 3: The total amount of each component contained in the resin composition of this embodiment is melt-blended.

[0301] In particular, some thermoplastic resins, such as (Aa) polyphenylene ether resin contained in component (A), and the raw material titanium dioxide are in powder form, resulting in poor bite-in properties in the extruder and difficulty in increasing production per unit time. Furthermore, the resin is prone to thermal degradation due to the longer residence time in the extruder. In summary, compared with the resin composition obtained by manufacturing method 3, the resin composition obtained by manufacturing methods 1 and 2 above exhibits improved bite-in properties of titanium dioxide, excellent mixability of the components, reduced decomposition, crosslinking, or carbide formation caused by thermal degradation, and increased resin production per unit time, thus yielding a resin composition with excellent productivity and quality, which is therefore more preferable.

[0302] [Injection molded parts, antenna components]

[0303] The injection-molded article of this embodiment is composed of the above-described thermoplastic resin composition. The manufacturing method of the injection-molded article of this embodiment is not particularly limited except for injection molding. Injection foaming can also be performed during injection molding to further achieve weight reduction. Both chemical foaming and physical foaming are effective and contribute to weight reduction.

[0304] Furthermore, it is assumed that the injection-molded body manufactured using such a method is used in a form in which a metal coating is formed on the surface.

[0305] The antenna component of this embodiment has one or more of the above-described injection-molded articles. The antenna component may have a structure formed by the interlocking of multiple molded articles.

[0306] In the antenna component of this embodiment, by having the injection-molded body described above, the unfolding of components in the antenna component, particularly antenna filters, antenna elements (vibrators), and other parts that require plating and are exposed to high temperatures, becomes easier. In particular, by using a material whose expansion coefficient shows the relationship between two adjacent temperature zones specified in this embodiment, it is possible to prevent the metal coating from peeling off and its shape from changing when the temperature rises, which is preferable.

[0307] [Metal coating of antenna components]

[0308] There is no particular limitation on the method for metallizing at least a portion of the aforementioned antenna components, and existing known methods can be used. The metallization 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) using an oxidizing agent such as permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, or nitric acid to form raised anchor points. As an oxidizing agent, an aqueous solution of sodium hydroxide (alkaline permanganate solution) such as potassium permanganate or sodium permanganate is particularly preferred. Then, a method combining electroless plating and electrolytic plating is used to form the metallization. Alternatively, a plating resist with a pattern opposite to the desired metallization pattern can be formed, and the metallization can be formed solely by electroless plating. As for the subsequent pattern formation method, subtractive or semi-additive methods known to those skilled in the art can be used, for example.

[0309] For dry deposition, known methods such as evaporation, sputtering, and ion plating can be used. Commonly cited methods include physical vapor deposition (PVD), chemical vapor deposition (CVD), and liquid phase growth. For example, PVD methods include vacuum evaporation, molecular beam epitaxy (MBE), sputtering, ion deposition, laser ablation, and ion cluster beam methods. CVD methods include thermal CVD, plasma CVD, metal-organic CVD (MOCVD), chemical transport (CVT), and substrate reaction methods. Liquid phase growth methods include liquid phase epitaxy, mobile solvent methods, and source current control methods. Other methods include electroless deposition. Among these methods, vacuum evaporation, sputtering, and plasma CVD are preferred due to their advantages in film thickness control, film quality control, versatility, and productivity.

[0310] Vacuum evaporation is a method that uses an electron beam and a resistance heater to heat and evaporate a target for film formation, depositing the film onto a substrate. Preferably, the initial vacuum level during decompression to evaporation is 1 × 10⁻⁶. -2 Pa or less, preferably 1×10 -3 After Pa, Evaporation deposition is performed.

[0311] Sputtering is a method in which high-energy particles, such as argon ions, supplied by an ion beam from a non-thermal equilibrium glow discharge plasma atmosphere or ion source, collide with a target for a film, resulting in target-emitted particles that are deposited on a substrate to form a film.

[0312] Plasma-CVD is a widely used method for forming hydrogenated amorphous Si films. For example, it involves decomposing silane (SiH4) gas through high-frequency glow discharge and depositing it onto a substrate to form a film. The total discharge pressure is 0.1–1 torr (13–130 Pa), the gas concentration is above 10% when diluted with argon or hydrogen, the gas flow rate is 50–200 mL / min, and the input power is tens to hundreds of mW / cm². 2 .

[0313] The metal used in the metal coating of this embodiment is not particularly limited, but copper or gold with high electrical conductivity are preferred.

[0314] [Circuit configuration of antenna components]

[0315] In this embodiment, the antenna component is sometimes coated or plated with metallic ink for use.

[0316] The antenna component of this embodiment may have one or more of the following components selected from the group consisting of metal circuits, metal wiring, and metal base.

[0317] From this perspective, an injection molded body capable of being coated with metallic ink is preferably used as the injection molded body in this embodiment. Regarding the metallic ink, gold, silver, and copper can all be used. Furthermore, inks containing multiple metals can also be used.

[0318] Regarding plating, any metal can be used. From an electrical conductivity perspective, copper is preferred, but lead, tin, gold, and silver can also be used.

[0319] The antenna component of this embodiment has a high resistance to copper damage and a low water absorption rate, thus reducing cracks after the above-mentioned metal ink is applied or plated.

[0320] For example, there are methods that bond metallic ink to resin using various methods after coating. Even methods requiring heat resistance, such as those using laser bonding, can be used for the antenna component of this embodiment.

[0321] For example, in antenna components, inkjet printing can be used to draw and form the circuit pattern of the wiring board using a conductive metal paste. This circuit pattern formation method can be referred to by known methods (for example, see Japanese Patent Application Laid-Open No. 2002-324966).

[0322] The conductive metal paste used is a conductive metal paste formed by uniformly dispersing fine-sized metal ultraparticles in a thermosetting resin composition containing an organic solvent. The average particle size of the fine-sized metal ultraparticles is selected in the range of 1 to 100 nm. The material can be formed by coating the surface of the metal ultraparticles with one or more compounds having groups containing nitrogen, oxygen, and sulfur atoms as groups that can coordinate and bind with the metal elements contained in the metal ultraparticles.

[0323] The conductive metal paste may contain fine metal microparticles with a fine average particle size, which may be composed of particles made of one metal selected from the group consisting of gold, silver, copper, platinum, palladium, tungsten, nickel, tantalum, bismuth, lead, indium, tin, zinc, titanium, and aluminum, or particles made of an alloy of two or more metals.

[0324] The method for forming a circuit pattern includes the following steps: spraying and coating the conductive metal paste into tiny droplets onto a substrate to depict a circuit pattern formed by the coating film of the conductive metal paste; and heating the depicted conductive metal paste coating film at a temperature at which at least the thermosetting resin is thermosetting.

[0325] As inkjet-based drawing methods, there are thermal drawing methods that generate bubbles by heating and foaming to expel droplets, and piezoelectric drawing methods that expel droplets by compressing piezoelectric elements.

[0326] In the case of forming a circuit by plating, there is a method that can selectively perform copper, nickel, or other plating treatment on the laser irradiation part.

[0327] [Dielectric properties of antenna components]

[0328] The antenna component of this embodiment is particularly suitable for applications requiring materials with low dielectric loss tangent in high-frequency regions. In these applications, increased loss degrades the performance of components used in communication devices, making the control of the dielectric loss tangent a crucial technology. According to this embodiment, an antenna component molded by injection molding can be provided that maintains tight adhesion to the metal coating while exhibiting minimal dimensional changes and dielectric loss tangent variations in high-temperature regions.

[0329] The antenna components of this embodiment can handle information at all frequencies from low to high, and therefore can be used as filters or antenna elements (vibrator components) for antennas in communication equipment. In particular, because they can maintain various characteristics and perform these characteristics in low-temperature, high-temperature, or humid environments, they can be suitable for use in heavy-duty antenna base stations for both outdoor and indoor applications.

[0330] Example

[0331] The following examples and comparative examples further illustrate this embodiment in detail, but this embodiment is not limited to these examples.

[0332] It should be noted that the raw materials and evaluation methods used in the embodiments and comparative examples are as follows.

[0333] [raw materials]

[0334] (Aa) Polyphenylene oxide (hereinafter referred to as PPE)

[0335] (Aa-1) Polyphenylene ether resin obtained by oxidative polymerization of 2,6-xylenol.

[0336] The specific viscosity of this polyphenylene ether resin (0.5 g / dL, chloroform solution, measured at 30°C) is 0.52 dL / g. The Tg is approximately 210°C.

[0337] (Aa-2) Polyphenylene ether resin obtained by oxidative polymerization of 2,6-xylenol.

[0338] The specific viscosity of this polyphenylene ether resin (0.5 g / dL, chloroform solution, measured at 30°C) is 0.40 dL / g. The Tg is approximately 210°C.

[0339] (Aa-3) Polyphenylene ether resin obtained by oxidative polymerization of 2,6-xylenol.

[0340] The specific viscosity of this polyphenylene ether resin (0.5 g / dL, chloroform solution, measured at 30°C) is 0.32 dL / g. The Tg is approximately 210°C.

[0341] (Ab) Crystalline resin

[0342] (Aba) Polyamide

[0343] (Aba-1) Polyamide 6,6 (hereinafter referred to as PA66)

[0344] 2400g of an equimolar salt of adipic acid and hexamethylenediamine, 100g of adipic acid, and 2.5L of pure water were added to a 5L autoclave and stirred thoroughly. After completely purging the autoclave atmosphere with nitrogen, the temperature was raised from room temperature to 220°C over approximately 1 hour with stirring. At this point, the gauge pressure inside the autoclave was 1.76MPa under the natural pressure of water vapor. Heating continued while removing water from the reaction system, ensuring the pressure did not exceed 1.76MPa. Further, after 2 hours, when the internal temperature reached 260°C, the internal pressure was reduced to 0.2MPa over approximately 40 minutes by opening and closing the autoclave valve while continuing heating. The mixture was then cooled to room temperature over approximately 8 hours. After cooling, the autoclave was opened, and approximately 2kg of the polymer was removed and pulverized.

[0345] The obtained polyamide has Mw = 38700 and Mw / Mn = 2.1. It should be noted that Mw and Mn were calculated using GPC (mobile layer: hexafluoroisopropanol, standard substance: PMMA (polymethyl methacrylate)).

[0346] Furthermore, the concentration of the terminal amino group was determined according to the method for determining the terminal amino group concentration described in the examples of Japanese Patent Application Publication No. 7-228689, and the result was a terminal amino group concentration of 38 μmol / g. The Tg was approximately 50°C.

[0347] (Aba-2) Polyamide 9,T (hereinafter referred to as PA9T).

[0348] 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 relative to the raw materials) and 5L of distilled water were added to a 40L autoclave for nitrogen purging.

[0349] Stir at 100℃ for 30 minutes, then raise the internal temperature to 210℃ over 2 hours. At this point, pressurize the autoclave to 22 kg / cm³. 2 After maintaining this state for another hour, the temperature was increased to 230°C, and then maintained at 230°C for 2 hours while slowly releasing water vapor and keeping the pressure at 22 kg / cm². 2 The reaction proceeds simultaneously. Next, the pressure is reduced to 10 kg / cm² over 30 minutes. 2The reaction was further carried out for 1 hour to obtain a prepolymer with an intrinsic viscosity [η] of 0.25 dl / g. This prepolymer was dried at 100°C under reduced pressure for 12 hours and pulverized to a size of less than 2 mm. It was then subjected to solid-state polymerization at 230°C and 0.1 mmHg for 10 hours, resulting in a melting point of 306°C and an intrinsic viscosity [η] of 0.80 dl / g. Furthermore, the concentration of the terminal amino groups was determined according to the method described in the examples of Japanese Patent Application Publication No. 7-228689, and the concentration of the terminal amino groups was found to be 20 μmol / g. The Tg was approximately 125°C.

[0350] (Abb) Polypropylene

[0351] (Abb-1) Polypropylene MFR = 2 g / 10 min polypropylene homopolymer

[0352] It should be noted that the MFR was determined according to ISO 1133 at a temperature of 230°C and a load of 2.16 kg. The Tg was approximately 0°C.

[0353] (Abb-2) Polypropylene modified with maleic anhydride, with a number-average molecular weight (Mn) of 60,000 and a weight-average molecular weight (Mw) of 91,000. Tg is approximately 0°C.

[0354] (Abc) Polyphenylene sulfide resin

[0355] (Abc-1): Linear PPS with repeating units of p-phenylene sulfide, with a melt viscosity (measured using a flow tester at 300°C, load 196 N, L / D = 10 / 1 for 6 minutes) of 30 Pa·s, based on an extraction amount of 0.7% by mass of dichloromethane and an -SX base of 32 μmol / g. Tg is approximately 80°C.

[0356] (Abc-2): Cross-linked PPS with a melt viscosity (measured using a flow tester at 300°C, load 196 N, L / D = 10 / 1 for 6 minutes) of 60 Pa·s and a volatile content of 160 ppm by mass of PPS in the molten state at 320°C. Tg is approximately 80°C.

[0357] (Ac) Amorphous thermoplastic resins other than polyphenylene ether

[0358] (Aca) Polystyrene resins

[0359] (Aca-1) High-impact polystyrene (manufactured by PS Japan Co., Ltd., H9405) has a Tg of approximately 100°C.

[0360] (Aca-2) High-impact polystyrene (manufactured by PETRO-CHEMICALS Co., Ltd., trade name "CT-60") has a Tg of approximately 100°C.

[0361] (Aca-3) Polystyrene (GPPS 680 manufactured by PS Japan Co., Ltd.) has a Tg of approximately 100°C.

[0362] (Acb) comprises a block copolymer containing at least one block primarily composed of an aromatic vinyl monomer unit and at least one block primarily composed of a conjugated diene monomer unit, and / or a hydride of the block copolymer.

[0363] (Acb-1) Hydrogenated block copolymer (Manufactured by Asahi Kasei Corporation, Tuftec (trademark) H1051)

[0364] (Acb-2) Hydrogenated block copolymer (Manufactured by Asahi Kasei Corporation, Tuftec (trademark) H1081)

[0365] (Acb-3)

[0366] A block copolymer with a II-I-II-I block structure, consisting of polymer block I made of polystyrene and polymer block II made of polybutadiene, was synthesized using a known method. The synthesized block copolymer was then hydrogenated using a known method. No polymer modification was performed. The physical properties of the resulting unmodified hydrogenated block copolymer are shown below.

[0367] Polystyrene content in the hydrogenated block copolymer: 44% by mass; Number-average molecular weight (Mn): 95,300; Weight-average molecular weight (Mw): 113,600; 1,2-vinyl bond content (total vinyl bond content) in the hydrogenated polybutadiene blocks: 79%; Hydrogenation rate relative to the polybutadiene moieties constituting the polybutadiene blocks: 99%.

[0368] (Acb-4)

[0369] Styrene-ethylene-propylene-styrene block copolymer elastomer (manufactured by KURARAY Corporation, SEPTON2023)

[0370] (Acc) Ethylene-α-olefin copolymer

[0371] (Acc-1) Ethylene-α-olefin copolymer (Mitsui Chemicals, Ltd., TAFMER P-0680J)

[0372] (Acd)styrene-glycidyl methacrylate copolymer

[0373] (Acd-1) A styrene-glycidyl methacrylate copolymer containing 5% by mass of glycidyl methacrylate (weight average molecular weight: 110,000)

[0374] (Ace) Thermoplastic Norbornene Resin

[0375] (Ace-1) thermoplastic norbornene resin (manufactured by Zeon Corporation, Japan, ZEONEX 480) has a Tg of approximately 140°C.

[0376] (B) Inorganic fillers

[0377] (B-1) Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., ECS03-T249)

[0378] (B-2) Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., ECS03-T747)

[0379] (B-3) Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., ECS03-T497)

[0380] (B-4) Talc (Haitoron A, manufactured by Takehara Chemical Industry)

[0381] (B-5) Talc (Lin Huacheng Industrial Manufacturing Talcan Powder PK-C)

[0382] (B-6) Glass flakes (Made by Nippon Sheet Glass, "Fleka REFG-301")

[0383] (B-7) Glass flakes (Made by Nippon Sheet Glass MEG160FY M06)

[0384] (Other ingredients)

[0385] (C-1) Ethylene bis-stearamide (manufactured by Kao Corporation, "KAO WAXEB-G")

[0386] (C-2) Maleic anhydride (manufactured by Nippon Oil & Fat Co., Ltd., "Crystal MAN")

[0387] (C-3) Peroxide (manufactured by Nippon Yushi Co., Ltd., "PERHEXA 25B-40")

[0388] [Evaluation Method]

[0389] The evaluation tests conducted in the examples and comparative examples are as follows.

[0390] (1-1), (1-2) Dielectric constant and dielectric loss tangent at 1 GHz

[0391] The obtained resin composition granules were fed into a small injection molding machine (trade name: EC75-SXII, manufactured by TOSHIBA MACHINE) with the barrel temperature set to 250–350°C. A 60mm × 60mm × 2.0mm plate was produced under the following conditions: mold temperature 70–130°C, injection pressure 200MPa, extrusion time 20 seconds, and cooling time 15 seconds. The plate was then cut, and measurements were taken under the following conditions.

[0392] Measurement Apparatus: HP8510C Vector Network Analyzer (Agilent Technologies)

[0393] HP83651A composite scanner (same as above)

[0394] Test set HP8517B (same as above)

[0395] Test piece dimensions: 40mm × 4mm × 2.0mm

[0396] The resonator is a cylindrical shape with an inner diameter of 229 mm and a height of 40 mm.

[0397] Measurement direction: Direction 1

[0398] Measurement frequency: around 1 GHz (TM010 mode)

[0399] Pretreatment: 90h / 22±1℃ / 60±5%RH

[0400] Test environment: 22℃ / 56%RH

[0401] The lower the dielectric loss tangent, the better the performance.

[0402] (1-3), (1-4) Dielectric constant-dielectric loss tangent at 28 GHz

[0403] The obtained resin composition granules were fed into a small injection molding machine (trade name: EC75-SXII, manufactured by TOSHIBA MACHINE) with the barrel temperature set to 250-350°C. A 150mm×150mm×4.0mm plate was produced under the conditions of mold temperature 70-130°C, injection pressure 200MPa, extrusion time 20 seconds, and cooling time 20 seconds. The dielectric constant at 28 GHz was measured under the following conditions.

[0404] Measurement frequency: 22GHz-33GHz

[0405] Measurement method: Frequency variation method

[0406] Measurement apparatus: Vector network analyzer (Keysight PNA N5247B 10MHz-67GHz), Keycom high-frequency free-space S-parameter measuring fixture, control PC

[0407] Measurement environmental conditions: room temperature 26℃, humidity 50%.

[0408] (1-5) Dielectric loss tangent after water absorption

[0409] The obtained resin composition granules were fed into a small injection molding machine (trade name: EC75-SXII, manufactured by TOSHIBA MACHINE) with the barrel temperature set to 250-350°C. A 60mm×60mm×0.9mm plate was produced under the conditions of mold temperature 70-130°C, injection pressure 200MPa, extrusion time 20 seconds, and cooling time 20 seconds. After immersion in warm water at 80°C for 144 hours, the dielectric loss tangent at 10GHz was measured under the following conditions.

[0410] Measurement frequency: 10GHz

[0411] Measurement apparatus: 10MHz to 43.5GHz PNA network analyzer N5224B, 10GHz discrete dielectric resonator N1501AE10

[0412] Measurement environmental conditions: room temperature 23℃, humidity 50%

[0413] (2) Load flexural temperature (DTUL)

[0414] The obtained resin composition granules were fed into a small injection molding machine (trade name: EC75-SXII, manufactured by TOSHIBA MACHINE) with the barrel temperature set to 250–350°C. An ISO dumbbell-shaped specimen for evaluation was produced using a mold under the following conditions: mold temperature 70–130°C, injection pressure 200 MPa, extrusion time 20 seconds, cooling time 15 seconds, and according to ISO dumbbell-shaped specimen molding conditions. This ISO dumbbell-shaped specimen was then cut to produce a specimen for DTUL (Deflection Temperature Under Load) measurement. The DTUL (ISO 75: 1.80 MPa load) was measured using the aforementioned DTUL specimen.

[0415] The higher the value, the better the heat resistance.

[0416] (3) Coating properties

[0417] The obtained resin composition granules were fed into a small injection molding machine (trade name: EC75-SXII, manufactured by TOSHIBA MACHINE) with the barrel temperature set to 250–350°C. A 90mm × 50mm × 2.5mm plate was produced under conditions of a mold temperature of 70–130°C, an injection pressure of 200 MPa, an extrusion time of 20 seconds, and a cooling time of 15 seconds. This plate was then etched with chromic acid and subsequently electroless copper plating was performed. The plate was marked as 0 if the entire surface was plated, and × if it was not plated. A higher degree of plating was considered superior for use as a component in communication equipment.

[0418] Furthermore, for the plating, after a thermal cycling test of 30 cycles of 60 minutes each between -30℃ and 85℃, incisions were made using a cutter marked with an "X". Then, celluloid (registered trademark) tape was applied, and a peel test was conducted. At this point, cases where the plating did not peel visually were recorded as "0", and cases where peeling was visually observed were recorded as "X". The less peeling occurred, the better the component was considered for use in communication equipment. In determining whether the plating had peeled, the celluloid (registered trademark) tape was applied, and the resin surface was observed in at least 10% of the peeled area (100%).

[0419] (4) Temperature dependence of dielectric loss tangent at 28 GHz

[0420] The obtained resin composition granules were fed into a small injection molding machine (trade name: EC75-SXII, manufactured by TOSHIBA MACHINE) with the barrel temperature set to 250–350°C. A 60mm × 60mm × 0.9mm plate was produced under the following conditions: mold temperature 70–130°C, injection pressure 250 MPa, extrusion time 20 seconds, and cooling time 15 seconds. This plate was then cut to 37mm × 37mm × 0.9mm, and the dielectric loss tangent was measured using the following apparatus. When the material's DTUL (Dielectric Loss Parameter) is between 120°C and 140°C, the dielectric loss tangent at 23°C was compared with that at 120°C. When the material's DTUL is above 140°C, the dielectric loss tangent at 23°C was compared with that at 140°C. The smaller these differences, the better the material is considered for use as a component in communication equipment.

[0421] Measurement apparatus: Keysight Technologies N5227B PNA microwave network analyzer 67GHz

[0422] Resonator; FATEC balanced disk resonator

[0423] Thermostatic bath: Espec SU-662

[0424] (5) Expansion rate

[0425] The obtained resin composition granules were fed into a small injection molding machine (trade name: EC75-SXII, manufactured by TOSHIBA MACHINE) with the barrel temperature set to 250–350°C. Evaluation ISO dumbbell-shaped specimens were produced using a mold under conditions of mold temperature 70–130°C, injection pressure 200 MPa, extrusion time 20 seconds, cooling time 15 seconds, and according to ISO dumbbell-shaped specimen molding conditions. Furthermore, the ISO dumbbell-shaped specimens were then processed... Figure 1 The test piece was cut out as shown and left to stand for 168 hours in a laboratory conditioned to 23°C and 50% RH. The expansion rate was then determined using a thermomechanical analysis apparatus (TMA, trade name TMA / SS6100, manufactured by SII Technologies) under the following conditions, according to the method described in ISO 11359.

[0426] After annealing at 100°C for 4 hours, the material was cooled to -40°C under a nitrogen atmosphere (flow rate 100 ml / min) and a compression load of 3 gf. Then, it was heated to 150°C at a rate of 5°C / min, and the expansion rate in the TD direction was measured. Regarding the expansion rate, the temperature range from -30°C to 120°C was divided into 15 temperature zones with 10°C intervals, and measurements were taken in each zone.

[0427] Furthermore, among the expansion rates of the 15 temperature regions, the highest expansion rate was taken as the maximum expansion rate (mm / mm / ℃), and the average expansion rate of the 15 temperature regions was calculated and taken as the average expansion rate (mm / mm / ℃).

[0428] In addition, among the 15 temperature regions, when the lower temperature side of any two adjacent temperature regions is taken as the lower temperature region and the higher temperature side is taken as the higher temperature region, the change ratio of the expansion ratio of the lower temperature region and the higher temperature region is calculated using the following formula based on the expansion ratio of the lower temperature region (expansion ratio of the lower temperature region (mm / mm / ℃)) and the expansion ratio of the higher temperature region (expansion ratio of the higher temperature region (mm / mm / ℃)). The value with the largest change ratio is taken as the maximum value (%) of the change ratio.

[0429] (The ratio of the change in expansion rate between the low-temperature region and the high-temperature region) = (Expansion rate of the high-temperature region - Expansion rate of the low-temperature region / Expansion rate of the low-temperature region) × 100

[0430] The above-mentioned any two adjacent temperature regions refer to 14 combinations of adjacent temperature regions (e.g., a combination of a low temperature region from -30℃ to -20℃ and a high temperature region from -20℃ to -10℃, a combination of a low temperature region from -20℃ to -10℃ and a high temperature region from -10℃ to 0℃, etc.) among 15 temperature regions (from -30℃ to -20℃, from -20℃ to -10℃, from -10℃ to 0℃, etc.) in which the temperature range from -30℃ to 120℃ is divided into 15 temperature regions with intervals of 10℃.

[0431] (6) Antenna efficiency at high and low temperatures

[0432] Antenna efficiency was simulated under the following conditions.

[0433] Antenna substrate: 60×7×1mm 3 Solid GND throughout, pattern width 1mm, thickness 25μm.

[0434] Copper + Ni plating

[0435] Main base plate: 60×130×1mm 3 Dielectric constant 4.0, dielectric loss 0.020

[0436] Thickness 35μm, conductivity 5.8×10 7 S / m

[0437] Simulation device: CST's MW STUDIO

[0438] Adjustments should be made at a reflection coefficient of 6dB or less within the operating frequency band.

[0439] Dielectric properties of materials (dielectric constant and dielectric loss tangent)

[0440] The dielectric properties of the material were determined using method (4).

[0441] <High Temperature Zone>

[0442] Use the following values ​​based on the DTUL value of the material.

[0443] Dielectric properties of a material with a DTUL value below 120°C at 100°C

[0444] Dielectric properties of the material at 120°C when the DTUL is between 120°C and 140°C.

[0445] Dielectric properties at 140°C when the DTUL of the material is above 140°C

[0446] <Low Temperature Region>

[0447] Dielectric properties at -30℃.

[0448] Furthermore, the total efficiency at 4GHz was obtained from the simulation and used as the antenna efficiency. The closer the total efficiency is to 0, the better the antenna is, indicating high performance.

[0449] [Examples 1-13, Comparative Examples 1-5]

[0450] Thermoplastic resin (A) and other components were blended according to the composition shown in Table 1, and the resin composition was manufactured using a twin-screw extruder ZSK-40 (manufactured by COPERION WERNER & PFLEIDERER, Germany). In this twin-screw extruder, a first feed port was provided upstream in the flow direction of the raw materials, a first vacuum exhaust port was provided downstream therefrom, a second feed port was provided midway, a third feed port was provided downstream therefrom, and a second vacuum exhaust port was provided further downstream therefrom.

[0451] Using an extruder set as described above, each component is added according to the composition and addition method shown in Tables 1 and 2. The mixture is melt-blended under the conditions of extrusion temperature of 250-320°C, screw speed of 300 rpm, and discharge rate of 100 kg / hour to produce granules.

[0452] The above evaluations were performed using the obtained resin composition granules. The evaluation results are shown in Tables 1 and 2.

[0453]

[0454] [Table 2]

[0455]

[0456] Industrial applicability

[0457] The antenna component of the present invention can be suitably used in antenna filters and antenna elements (vibrators), etc., and has industrial applicability. In particular, it can be suitably used as an antenna component that can maintain tight adhesion to the metal coating, while exhibiting small dimensional changes and dielectric loss tangent changes in high-temperature regions, can be injection molded, and is applicable in all environments such as low temperature, high temperature, and humidity.

Claims

1. An antenna component having an injection-molded body composed of a thermoplastic resin composition, wherein at least a portion of the injection-molded body is metal-coated for use, wherein... The thermoplastic resin composition comprises (A) a thermoplastic resin, wherein (A) the thermoplastic resin comprises (Aa) a polyphenylene ether resin. The DTUL of the thermoplastic resin composition is above 120°C. The temperature of the thermoplastic resin composition when the temperature is increased from -30°C to 120°C is divided into temperature regions with intervals of 10°C. When the lower temperature side of two adjacent temperature regions is designated as the low temperature region and the higher temperature side as the high temperature region, in any two adjacent temperature regions, the expansion rate (mm / mm / °C) of the resin composition in the TD direction in the low temperature region, measured using the method described in ISO 11359, and the expansion rate (mm / mm / °C) of the resin composition in the TD direction in the high temperature region, measured using the method described in ISO 11359, both satisfy the following relationship: -50≤((linear expansion rate of high temperature region-linear expansion rate of low temperature region) / linear expansion rate of low temperature region)×100≤50.

2. The antenna component as claimed in claim 1, wherein, The temperature dependence of the thermoplastic resin composition on the dielectric loss tangent at 28 GHz satisfies the following condition: Condition 1: When the DTUL is above 120°C and below 140°C, the difference between the dielectric loss tangent at 23°C and the dielectric loss tangent at 120°C is less than 0.

004. Condition 2: When the DTUL is above 140°C, the difference between the dielectric loss tangent at 23°C and the dielectric loss tangent at 140°C is less than 0.

004.

3. The antenna component as described in claim 1 or 2, wherein, The temperature of the thermoplastic resin composition, as it is heated from -30°C to 120°C, is divided into temperature zones spaced 10°C apart. The average linear expansion rate of the resin composition in the TD direction, measured according to ISO 11359, for each temperature zone is 10 × 10⁻⁶. -5 Below mm / mm / ℃.

4. The antenna component as claimed in claim 3, wherein, The temperature of the thermoplastic resin composition, as it is heated from -30°C to 120°C, is divided into temperature zones spaced 10°C apart. The maximum linear expansion rate of the resin composition in the TD direction, measured according to ISO 11359, is 10 × 10⁻⁶ for each temperature zone. -5 Below mm / mm / ℃.

5. The antenna component as claimed in claim 1 or 2, wherein, The (A) thermoplastic resin comprises (Ab) crystalline resin.

6. The antenna component as claimed in claim 1 or 2, wherein, The thermoplastic resin composition contains more than 10% by weight of (B) inorganic filler.

7. The antenna component as claimed in claim 1 or 2, wherein, The (A) thermoplastic resin contains more than 10% by weight of (Aa) polyphenylene ether resin.

8. The antenna component as described in claim 1 or 2, which is used in an outdoor or indoor antenna base station.

9. The antenna component as described in claim 1 or 2, wherein a metal coating is formed by electroless copper plating via chromate etching.

10. The antenna component as claimed in claim 1 or 2, wherein, After a metal coating is formed by electroless copper plating with chromic acid etching, the metal coating layer does not crack after being placed at 85°C and 85% humidity for 2000 hours.

11. The antenna component as claimed in claim 1 or 2, wherein, The thermoplastic resin composition comprises (Aca) polystyrene-based resin.

12. The antenna component as claimed in claim 1 or 2, wherein, The thermoplastic resin composition comprises (Acb) a block copolymer comprising at least one block of an aromatic vinyl monomer unit and at least one block of a conjugated diene monomer unit and / or a hydrogenation of the block copolymer.

13. The antenna component as claimed in claim 5, wherein, The (Ab) crystalline resin is at least one selected from the group consisting of (Aba) polyamide, (Abb) polypropylene and (Abc) polyphenylene sulfide resin.

14. The antenna component as claimed in claim 5, wherein, The content of the (Ab) crystalline resin is less than 80% by mass relative to the thermoplastic resin composition.

15. The antenna component as claimed in claim 11, wherein, The content of the (Aca) polystyrene resin is 0 to 100 parts by weight relative to 100 parts by weight of the (Aa) polyphenylene ether resin.

16. The antenna component as claimed in claim 12, wherein, The content of the (Acb) component is 1 to 40 parts by mass relative to 100 parts by mass of the (Aa) polyphenylene ether resin.

17. The antenna component as claimed in claim 1 or 2, wherein, The thermoplastic resin composition comprises (Acc) ethylene-α-olefin copolymer.

18. The antenna component as claimed in claim 1 or 2, wherein, The thermoplastic resin composition comprises (Acd) styrene-glycidyl methacrylate copolymer.

19. The antenna component as claimed in claim 1 or 2, wherein, The temperature of the thermoplastic resin composition when the temperature is increased from -30°C to 120°C is divided into temperature regions with intervals of 10°C. When the lower temperature side of two adjacent temperature regions is designated as the low temperature region and the higher temperature side as the high temperature region, in any two adjacent temperature regions, the expansion rate (mm / mm / °C) of the resin composition in the TD direction in the low temperature region, measured using the method described in ISO 11359, and the expansion rate (mm / mm / °C) of the resin composition in the TD direction in the high temperature region, measured using the method described in ISO 11359, both satisfy the following relationship: -40≤((expansion rate of high temperature region-expansion rate of low temperature region) / expansion rate of low temperature region)×100≤40.

20. The antenna component as claimed in claim 3, wherein, The temperature of the thermoplastic resin composition, when heated from -30°C to 120°C, was divided into temperature zones with intervals of 10°C. The average expansion rate of the resin composition in the TD direction, measured according to ISO 11359, was 9 × 10⁻⁶ for each temperature zone. -5 Below mm / mm / ℃.

21. The antenna component as claimed in claim 4, wherein, The temperature of the thermoplastic resin composition, as it is heated from -30°C to 120°C, is divided into temperature zones spaced 10°C apart. The maximum value of the expansion coefficient of the resin composition in the TD direction, measured according to ISO 11359, is 2 × 10⁻⁶. -5 mm / mm / ℃~8×10 -5 mm / mm / ℃.

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