Communication equipment component

Abstract

To provide a communication equipment component that has a suitable surface smoothness, excellent antenna performance, and excellent antenna performance even at high temperatures and in wet conditions.SOLUTION: The present invention provides a communication equipment component consisting of a conductive molded body including a resin molded body made of a thermoplastic resin composition and a conductive portion formed on the surface of the resin molded body, and the thermoplastic resin composition contains a polyphenylene ether resin and a laser direct structuring (LDS) additive, the thermoplastic resin composition has a Vicat softening temperature and water absorption rate within a predetermined range, and the conductive portion has a surface roughness Sa within a predetermined range.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to parts for communication devices. Specifically, the present invention relates to a part for a communication device comprising a resin molded body made of a thermoplastic resin composition containing a laser direct structuring additive, and a conductive part formed on the surface of the resin molded body.

Background Art

[0002] In recent years, with the weight reduction and miniaturization of mobile communication devices such as mobile phones, the requirements for weight reduction and miniaturization of each part used in communication devices such as dielectric antennas have been increasing. Therefore, a method for manufacturing an antenna capable of three-dimensional design for smartphones, wireless earphones, personal computers, etc. has been demanded.

[0003] As one of the technologies for forming such a three-dimensional antenna, laser direct structuring (LDS) has attracted attention. The LDS technology is, for example, as shown in FIGS. 1(a) to (d), a laser is irradiated on the surface of a molded product made of an LDS thermoplastic resin composition containing an LDS additive (FIG. 1(a)), only the irradiated portion is activated (FIG. 1(b)), and a metal is applied to the activated portion (FIG. 1(c)), thereby forming a conductive part (such as a plating layer) (FIG. 1(d)). The feature of this technology is that a metal structure such as an antenna can be directly manufactured on the surface of a resin base material without using an adhesive or the like, and miniaturization of parts becomes possible. Here, FIG. 2 illustrates the process of mounting a circuit by the LDS technology. After designing the circuit (FIG. 2(a)), a resin molded body is prepared (FIG. 2(b)), a laser is irradiated along the shape of the designed circuit (FIG. 2(c)), and then, by plating, a metal structure of a desired shape can be obtained (FIG. 2(d)).

[0004] Such LDS technology is disclosed, for example, in Patent Documents 1 to 3 and the like. LDS is one of the three-dimensional molded circuit component (3D-MID) technologies. Examples of components in use include antennas for smartphones, antennas for wearable devices, and antennas for automotive applications, which are disclosed in Non-Patent Document 1. In addition, photographs of examples of antennas are disclosed in Non-Patent Document 2.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Non-Patent Documents

[0006]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] In recent years, for parts for communication devices made of the thermoplastic resin composition for LDS as described above, it has been required to exhibit antenna characteristics in a high-frequency band of 1 GHz or higher, and for this purpose, it is required to have low dielectric characteristics. Furthermore, in recent years, with the spread of fifth-generation (5G) communication, communication base stations and smart devices capable of 5G communication have been demanded. As communication speeds increase, the heat generated by base stations and smart devices is increasing, so as antenna members, it has come to be required that they maintain the various characteristics described above and that they be exhibited even in high-temperature or humid environments.

[0008] Therefore, an object of the present invention is to provide a part for a communication device that is a part formed with a circuit by plating after surface processing a thermoplastic resin for LDS with a laser and that retains excellent antenna performance even at high temperatures and in humid conditions.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that a thermoplastic resin composition constituting a part for a communication device contains polyphenylene ether, and by adjusting the surface roughness of the conductive part within an appropriate range, the part for a communication device can exhibit excellent antenna performance even at high temperatures and in humid conditions, and have reached the present invention.

[0010] That is, the present invention is as follows. [1] A part for a communication device comprising a resin molded body made of a thermoplastic resin composition and a conductive part formed on the surface of the resin molded body, wherein the thermoplastic resin composition contains a polyphenylene ether-based resin and a laser direct structuring (LDS) additive, the thermoplastic resin composition has a Vicat softening temperature of 90°C or higher and a water absorption rate of 1.5% or less, the conductive part has a surface roughness Sa of 0.5 μm or more and 3 μm or less, A part for a communication device. [2] The component for a communication device according to [1], wherein the conductive portion is formed by laser direct structuring. [3] The LDS additive is (i) copper chromic acid, or (ii) a compound containing antimony and tin The component for a communication device according to [1] or [2], which contains the same. [4] The component for a communication device according to any one of [1] to [3], wherein the thermoplastic resin composition further contains at least one block mainly composed of an aromatic vinyl monomer unit and at least one block mainly composed of a conjugated diene monomer unit, and / or a hydrogenated product of the block copolymer. [5] The component for a communication device according to any one of [1] to [4], wherein the thermoplastic resin composition has a heat deflection temperature under load (DTUL) of 90 °C or higher. [6] The component for a communication device according to any one of [1] to [5], wherein the thermoplastic resin composition has a dielectric constant of 3.0 or less and a dielectric loss tangent of 0.008 or less. [7] The component for a communication device according to any one of [1] to [6], wherein the dielectric loss tangent after immersing the resin molded body in warm water at 80 °C for 144 hours is 0.03 or less. [8] The component for a communication device according to any one of [1] to [7], which is a component for an antenna.

Advantages of the Invention

[0011] According to the present invention, it is possible to obtain a component in which a circuit is formed by plating after surface processing of the thermoplastic resin for LDS with a laser, and it is possible to obtain a component for a communication device in which antenna performance is realized even under high temperature or humidity.

Brief Description of the Drawings

[0012]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0013] Hereinafter, the content of the present invention will be described in detail.

[0014] The component for a communication device of this embodiment is composed of a conductive molded body including a resin molded body made of a thermoplastic resin composition and a conductive part formed on the surface of the resin molded body.

[0015] [Thermoplastic Resin Composition, Resin Molded Body] The thermoplastic resin composition constituting the resin molded body contains (A) a matrix resin and (B) an LDS additive. By using the thermoplastic resin composition, it is possible to easily satisfy that "the conductive part has a surface roughness Sa of 0.5 μm or more and 3 μm or less".

[0016] ((A) Matrix Resin) The (A) matrix resin preferably contains (A-a) a polyphenylene ether-based resin, and optionally further contains at least one block mainly composed of (A-b) an aromatic vinyl monomer unit and at least one block mainly composed of a conjugated diene monomer unit, a block copolymer, and / or a hydrogenated product of the block copolymer.

[0017] The above-mentioned (A) matrix resin refers to the resin component excluding inorganic fillers and the like in the thermoplastic resin composition. Note that the (B) LDS additive described later is not included herein. Such resin components include at least (A-a) polyphenylene ether-based resin, and in addition, various resins used for molding, such as polyester-based resins, polyamide-based resins, polycarbonate-based resins, vinyl-based resins, olefin-based resins, acrylic-based resins, polyphenylene sulfide, aromatic-based resins, etc. can be further included.

[0018] ·(A-a) Polyphenylene ether-based resin Examples of the above-mentioned (A-a) polyphenylene ether-based resin (hereinafter sometimes simply referred to as "the above-mentioned (A-a) component") include a polyphenylene ether homopolymer having a repeating unit structure represented by the following formula (1) and a polyphenylene ether copolymer having a repeating unit structure represented by the following formula (1).

Chemical formula

[0019] Specific examples of the component (A-a) include polyphenylene ether homopolymers such as poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), and poly(2,6-dichloro-1,4-phenylene ether). Further, specific examples of the component (A-a) also include polyphenylene ether copolymers such as copolymers of 2,6-dimethylphenol and other phenols (for example, copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and copolymers of 2,6-dimethylphenol and 2-methyl-6-butylphenol as described in Japanese Patent Publication No. 52-17880).

[0020] Among these, particularly preferred as the component (A-a) are poly(2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or a mixture thereof.

[0021] Note that the component (A-a) may be used alone or in combination of two or more.

[0022] The method for producing the (A-a) polyphenylene ether-based resin is not particularly limited as long as it can be obtained by a known method. For example, a method described in U.S. Patent No. 3306874, which is produced by oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine as a catalyst, and methods described in U.S. Patent No. 3306875, U.S. Patent No. 3257357, U.S. Patent No. 3257358, Japanese Patent Laid-Open No. 50-51197, Japanese Patent Publication No. 52-17880, and Japanese Patent Laid-Open No. 63-152628, etc. can be mentioned.

[0023] The preferred range of the reduced viscosity of the (A-a) polyphenylene ether resin (measured with an Ubbelohde viscometer at 30 °C in a 0.5 g / dL chloroform solution) is 0.30 dL / g or more, more preferably 0.35 dL / g or more, most preferably 0.38 dL / g or more, 0.80 dL / g or less, more preferably 0.75 dL / g or less, and most preferably 0.55 dL / g or less. When the reduced viscosity of the (A-a) polyphenylene ether resin is within the above range, it has excellent properties such as impact resistance and heat resistance.

[0024] In the (A-a) polyphenylene ether resin, a blend of two or more polyphenylene ethers with different reduced viscosities can also be preferably used.

[0025] Also, for the stabilization of the (A-a) polyphenylene ether resin, various known stabilizers can also be preferably used. Examples of stabilizers include metal-based stabilizers such as zinc oxide and zinc sulfide, and organic stabilizers such as hindered phenol-based stabilizers, phosphorus-based stabilizers, and hindered amine-based stabilizers. The preferred compounding amount of these stabilizers is less than 5 parts by mass with respect to 100 parts by mass of the (A-a) polyphenylene ether resin.

[0026] Furthermore, known additives and the like that can be added to the (A-a) polyphenylene ether resin may also be added in an amount of less than 10 parts by mass with respect to 100 parts by mass of the (A-a) polyphenylene ether resin.

[0027] The (A-a) component may be a modified polyphenylene ether obtained by reacting the polyphenylene ether homopolymer and / or the polyphenylene ether copolymer with a styrene monomer or its derivative and / or an α,β-unsaturated carboxylic acid or its derivative. Here, the graft amount or addition amount of the styrene monomer or its derivative and / or the α,β-unsaturated carboxylic acid or its derivative is preferably 0.01 to 10% by mass with respect to 100% by mass of the component (A-a).

[0028] Examples of the method for producing the modified polyphenylene ether include a method of reacting in a molten state, a solution state, or a slurry state at a temperature of 80 to 350°C in the presence or absence of a radical generator.

[0029] As the polyphenylene ether, a mixture of the polyphenylene ether homopolymer and / or the polyphenylene ether copolymer and the modified polyphenylene ether in an arbitrary ratio may be used.

[0030] From the viewpoint of achieving both heat resistance and low dielectric constant and low dielectric tangent, the content of the polyphenylene ether-based resin of the component (A-a) with respect to 100 parts by mass of the matrix resin (A) is preferably 30 parts by mass or more, preferably 40 parts by mass or more, and more preferably 50 parts by mass or more. Also, from the viewpoint of moldability, the content is preferably 95 parts by mass or less.

[0031] ·(A-b) A block copolymer containing at least one block mainly composed of an aromatic vinyl monomer unit and at least one block mainly composed of a conjugated diene monomer unit, and / or a hydrogenated product of the block copolymer In the present embodiment, the matrix resin (A) may further contain a block copolymer containing at least one block mainly composed of an aromatic vinyl monomer unit (hereinafter sometimes simply referred to as "aromatic vinyl polymer block") and at least one block mainly composed of a conjugated diene monomer unit (hereinafter sometimes simply referred to as "conjugated diene polymer block"), and / or a hydrogenated product of the block copolymer (hereinafter sometimes simply referred to as the component (A-b)), and it is preferable to contain the component (A-b).

[0032] Regarding the above-mentioned aromatic vinyl polymer block, the phrase "mainly composed of aromatic vinyl monomer units" means that in the block, 50% by mass or more is aromatic vinyl monomer units. More preferably, the aromatic vinyl monomer units are 70% by mass or more, still more preferably 80% by mass or more, and most preferably 90% by mass or more.

[0033] Similarly, regarding the "mainly composed of conjugated diene monomer units" of the conjugated diene polymer block, it means that 50% by mass or more is conjugated diene monomer units. More preferably, the conjugated diene monomer units are 70% by mass or more, still more preferably 80% by mass or more, and most preferably 90% by mass or more.

[0034] In addition, the above-mentioned aromatic vinyl polymer block may be, for example, a copolymer block in which a small amount of conjugated diene compound is randomly bonded in the aromatic vinyl polymer block. Similarly, in the case of the above-mentioned conjugated diene polymer block, for example, it may be a copolymer block in which a small amount of aromatic vinyl compound is randomly bonded in the conjugated diene polymer block.

[0035] There is no particular limitation on the aromatic vinyl compound used to form the aromatic vinyl monomer unit. For example, styrene, α-methylstyrene, vinyltoluene, etc. may be mentioned, and one or more compounds selected from these are used. Among them, styrene is particularly preferred.

[0036] There is no particular limitation on the conjugated diene compound used to form the conjugated diene polymer block. For example, butadiene, isoprene, piperylene, 1,3-pentadiene, etc. may be mentioned, and one or more compounds selected from these are used. Among them, butadiene, isoprene and combinations thereof are preferred.

[0037] The microstructure of the conjugated diene polymer block portion of the block copolymer preferably has a 1,2-vinyl content or a total amount of 1,2-vinyl content and 3,4-vinyl content (total vinyl bond amount) of 5 to 80%, more preferably 10 to 70%.

[0038] The total vinyl bond amount can be measured using an infrared spectrophotometer.

[0039] The non-hydrogenated block copolymer used for the production of the hydrogenated product (hydrogenated block copolymer) of the block copolymer is preferably a block copolymer in which the aromatic vinyl polymer block (A) and the conjugated diene polymer block (B) have a bonding form selected from A-B type, A-B-A type, and A-B-A-B type. Among these, block copolymers having different bonding forms may be used in combination. Among these, it is more preferably a bonding form selected from A-B-A type and A-B-A-B type, and even more preferably an A-B-A type bonding form.

[0040] In addition, the (A-b) component used in this embodiment is preferably a partially hydrogenated block copolymer. The partially hydrogenated block copolymer refers to a product obtained by subjecting the above-mentioned non-hydrogenated block copolymer to a hydrogenation treatment, and controlling the aliphatic double bonds of the conjugated diene polymer block in a range exceeding 0% and less than 100%. The preferred hydrogenation rate of the partially hydrogenated block copolymer 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%.

[0041] Furthermore, the (A-b) component preferably has a number average molecular weight of 30,000 or more and less than 300,000. When the number average molecular weight of the (A-b) component is within this range, a thermoplastic resin composition excellent in fluidity, impact strength, and flame retardancy can be obtained.

[0042] The method for evaluating the number average molecular weight of the component (A-b) in the thermoplastic resin composition is shown below. That is, a solvent that shows good solubility in the component (A-b) and poor solubility in the (A-a) polyphenylene ether-based resin, such as chloroform, is used to separate the component (A-b) from the thermoplastic resin composition. The separated component (A-b) is measured using a gel permeation chromatography measurement device [GPC SYSTEM21: manufactured by Showa Denko K.K.] with an ultraviolet spectroscopic detector [UV-41: manufactured by Showa Denko K.K.], and the number average molecular weight is determined by conversion to standard polystyrene. The measurement conditions may be as follows [solvent: chloroform, temperature: 40 °C, column: sample side (K-G, K-800RL, K-800R), reference side (K-805L × 2), flow rate 10 mL / min, measurement wavelength: 254 nm, pressure 15 - 17 kg / cm 2 )].

[0043] Also, when measuring the number average molecular weight, low molecular weight components due to catalyst deactivation during polymerization may be detected. In that case, the low molecular weight components are not included in the molecular weight calculation. The low molecular weight components refer to components with a molecular weight of 3000 or less. Usually, the correctly calculated molecular weight distribution (weight average molecular weight / number average molecular weight) is in the range of 1.0 - 1.1.

[0044] These block copolymers as the component (A-b) that can be used in these embodiments may be mixed and used in two or more kinds for each of those with different bonding forms, different aromatic vinyl compound species, different conjugated diene compound species, different 1,2-vinyl contents or different 1,2-vinyl contents and 3,4-vinyl contents, different aromatic vinyl compound component contents, different hydrogenation rates, etc., as long as it does not go against the gist of this embodiment.

[0045] Also, these block copolymers as the component (A-b) that can be used in this embodiment may be block copolymers in which all or part is modified.

[0046] The modified block copolymer referred to herein means a block copolymer modified with at least one kind of modified compound having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or glycidyl group in its molecular structure.

[0047] As a method for producing the modified block copolymer, in the presence or absence of a radical initiator, (1) a method of melt-kneading and reacting with a modified compound in a temperature range of not less than the softening point temperature of the block copolymer and not more than 250 °C, (2) a method of reacting the block copolymer and the modified compound in a solution at a temperature below the softening point of the block copolymer, (3) a method of reacting the block copolymer and the modified compound without melting them at a temperature below the softening point of the block copolymer, etc. may be mentioned, and any of these methods may be used, but the method (1) is preferred, and further, among the methods (1), the method carried out in the presence of a radical initiator is most preferred.

[0048] As the "at least one kind of modified compound having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or glycidyl group in its molecular structure" referred to herein, the same modified compounds as those described for the modified polyphenylene ether can be used.

[0049] In addition, the content of the component (A-b) is preferably 1 to 40 parts by mass, more preferably 2 to 35 parts by mass, and still more preferably 2 to 30 parts by mass when the polyphenylene ether resin of the component (A-a) is 100 parts by mass.

[0050] Furthermore, the total content of the polyphenylene ether resin of the component (A-a) and the component (A-b) with respect to 100 parts by mass of the matrix resin of the component (A) is preferably 30 parts by mass or more, and more preferably 35 parts by mass or more. By setting the total content of the component (A-a) and the component (A-b) within the above range, heat resistance, low dielectric constant and low dielectric tangent can be achieved simultaneously, and the (B) LDS additive described later can be in any dispersion form.

[0051] · (A-c) Polystyrene resin The (A) matrix resin may further contain (A-c) polystyrene resin. Examples of the polystyrene resin 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 in which the styrene-acrylonitrile copolymer is rubber-reinforced. Among these, it is preferable to contain atactic polystyrene and / or high impact polystyrene. Note that the polystyrene resin may be used alone or in combination of two or more.

[0052] In the present embodiment, the preferable content of the (A-c) polystyrene resin is 0 to 100 parts by mass, more preferably 0 to 90 parts by mass, and still more preferably 0 to 80 parts by mass when the (A-a) polyphenylene ether resin is 100 parts by mass.

[0053] · Other resin components Examples of other resin components in the (A) matrix resin of the present embodiment include polyesters, polyolefins such as polypropylene, polyamides, polyphenylene sulfide, and olefinic thermoplastic elastomers.

[0054] Examples of the olefinic thermoplastic elastomer include polyolefin homopolymers such as polyethylene and polypropylene; polyolefin copolymers such as ethylene-propylene copolymer, ethylene-butylene copolymer, and ethylene-octene copolymer. In particular, examples of the polyethylene homopolymer include high-pressure low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE).

[0055] The specific preferred addition amounts of the other resin components, when the total amount of the thermoplastic resin composition is 100% by mass, are each 15% by mass or less, more preferably 13% by mass or less, and still more preferably 10% by mass or less.

[0056] Also, the preferred addition amount of the total of the other resin components is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less when the total amount of the thermoplastic resin composition is 100% by mass.

[0057] In particular, from the viewpoint of achieving low dielectric tangent and low dielectric constant, the total content of polyamide and polyphenylene sulfide with respect to 100 parts by mass of the (A) matrix resin is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 1 part by mass or less, and may even be 0 parts by mass. Furthermore, the thermoplastic resin composition may use virgin materials or recycled materials. The type of recycling may be either a material recycling material or a chemical recycling material, regardless of whether it is a PCR material or a PIR material.

[0058] ((B) LDS additive) The thermoplastic resin composition constituting the resin molded body of the communication device component of the present embodiment further contains a (B) laser direct structuring (LDS) additive in addition to the above-described (A) matrix resin. By including the (B) LDS additive, it becomes possible to form plating on the surface of the obtained resin molded product by the LDS technique, and a conductive portion can be formed on the surface. At this time, it is preferable that the dielectric constant and dielectric tangent of the thermoplastic resin composition with the conductive portion formed on the surface are lower, as the characteristics as an antenna become better. Also, in practical use, plating deposition properties for forming a conductive portion and adhesion of the deposited plating are required. In order to satisfy these, it is necessary to select an appropriate thermoplastic resin and LDS additive.

[0059] The LDS technology is a technique in which a resin molded body made of a thermoplastic resin composition is irradiated with a laser, and then the resin molded body is plated to selectively form plating only on the laser-irradiated portion of the surface of the resin molded body to obtain a conductive molded body. The LDS technology can be performed, for example, by irradiating a resin molded body made of a thermoplastic resin composition with a laser such as a pulsed laser of near-infrared light with a wavelength of 1064 nm under appropriate conditions such as an output of 7 W, a frequency of 50 kHz, and a speed of 2000 mm / s, and then immersing it in an electroless plating bath as a subsequent plating step to selectively form plating only on the laser-irradiated portion.

[0060] The (B) LDS additive refers to a compound that can form a conductive portion on the surface of a resin molded body by the LDS technology when added in a specific amount (about 3 to 15 parts by mass with respect to 100 parts by mass of the entire thermoplastic resin composition). From the viewpoint of enhancing the plating property, the (B) LDS additive preferably contains at least one of copper, antimony, tin, aluminum, and zinc, more preferably contains copper chromate and / or a compound containing antimony and tin (preferably an oxide), and even more preferably contains an oxide containing at least antimony and tin.

[0061] More specifically, the embodiment of the (B) LDS additive is an oxide containing at least one of antimony and phosphorus and tin, preferably an oxide containing antimony and tin. This is because a compound containing antimony and tin is easier to control the dispersion than the copper chromate compound, and thus stable dielectric constant and dielectric tangent values can be obtained. Furthermore, as the oxide containing antimony and tin, an oxide in which the content of tin is more than the content of antimony is more preferable, and an oxide in which the amount of tin relative to the total amount of tin and antimony is 80% by mass or more is even more preferable.

[0062] More specifically, examples of the (B) LDS additive include tin oxide doped with antimony, tin oxide doped with antimony oxide, tin oxide doped with phosphorus, and tin oxide doped with phosphorus oxide. Tin oxide doped with antimony and tin oxide doped with antimony oxide are preferred, and tin oxide doped with antimony oxide is more preferred.

[0063] The (B) LDS additive may be a synthetic product or a commercially available product. In addition, the commercially available product may be a substance sold for other uses as long as it meets the requirements of the LDS additive in this embodiment, in addition to those commercially available as the LDS additive. Note that only one type of the (B) LDS additive may be used, or two or more types may be used in combination.

[0064] In addition to antimony and tin, the (B) LDS additive may contain a trace amount of other metals. Examples of other metals include copper, chromium, lead, indium, iron, cobalt, nickel, zinc, cadmium, silver, bismuth, arsenic, manganese, magnesium, and calcium. These metals may exist as oxides. However, the content of metal oxides other than antimony and tin is preferably 30% by mass or less. In particular, copper chromate is preferably less than 5 parts by mass (not including 5 parts by mass or more) with respect to 100 parts by mass of the thermoplastic resin composition.

[0065] In addition, the content of the (B) LDS additive in the thermoplastic resin composition is preferably 1.0 part by mass or more, more preferably 2.0 parts by mass or more, still more preferably 3.0 parts by mass or more, even more preferably 5.0 parts by mass or more, and even more preferably 6.0 parts by mass or more, based on 100 parts by mass of the entire thermoplastic resin. By setting the content of the (B) LDS additive to 1.0 part by mass or more, the plating property tends to be further improved. Also, the content of the (B) LDS additive in the thermoplastic resin composition is preferably 30.0 parts by mass or less, more preferably 25.0 parts by mass or less, still more preferably 20.0 parts by mass or less, even more preferably 15.0 parts by mass or less, and even more preferably 12.0 parts by mass or less, based on 100 parts by mass of the thermoplastic resin. By setting the content of the (B) LDS additive to 30.0 parts by mass or less, the resin composition tends to exhibit a lower dielectric constant and lower dielectric tangent. Note that the thermoplastic resin composition may contain only one kind of the (B) LDS additive or may contain two or more kinds. When two or more kinds are contained, it is preferable that the total amount is within the above range.

[0066] ((F) Flame retardant) The thermoplastic resin composition may further contain an (F) flame retardant. (F) Flame retardants include inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide; nitrogen-containing cyclic compounds such as melamine, cyanuric acid, and their salts; organic phosphate esters such as triphenyl phosphate, triphenyl phosphate hydroxide, bisphenol A bis(diphenyl phosphate), and their derivatives; phosphorus-containing nitrogen compounds such as ammonium polyphosphate and melamine polyphosphate; phosphazene compounds described in JP-A-11-181429; boric acid compounds such as zinc borate; silicone oils; red phosphorus; phosphinates described in WO 2007 / 055147; mixtures thereof; and the like. Among them, nitrogen-containing cyclic compounds, organic phosphate esters, phosphorus-containing nitrogen compounds, phosphazene compounds, boric acid compounds, silicone oils, and phosphinates are preferred, and bisphenol A bis(diphenyl phosphate) and its derivatives, phosphinates, and mixtures thereof are more preferred.

[0067] As the phosphate ester as the flame retardant (F), there are those represented by the following formula (I) or (II).

Chemical formula

[0068] Note that the condensed phosphate ester represented by formula (II) has a smaller dipole moment than the condensed phosphate ester represented by formula (I), and thus has excellent dielectric properties.

[0069] Among them, from the viewpoint of the dipole moment, a preferred condensed phosphate ester contains 50% or more of a phosphate ester in which Q1, Q2, Q3, and Q4 in formula (II) are hydrogen or a methyl group, R1 is hydrogen, and the range of n is 1 to 3, particularly n is 1.

[0070] Incidentally, the flame retardant is generally commercially available, and examples thereof include products named CR-741, CR-747, CR733S, PX-200, etc. of Daihachi Chemical Industry Co., Ltd. The phosphates include at least one selected from the group consisting of a phosphate represented by the following formula (1), a diphosphate represented by the following formula (2), and condensates thereof.

[0071]

Chemical formula

[0072]

Chemical formula

[0073] Moreover, as the (F) flame retardant, an inorganic or organic flame retardant substantially free of halogen is preferable. In this specification, being substantially free of halogen means that the halogen concentration in the resin composition containing the (F) flame retardant is less than 2% by mass. The halogen concentration in the resin composition containing the (F) flame retardant is preferably less than 1% by mass, and more preferably less than 0.5% by mass.

[0074] The content of the (F) flame retardant can be in the range of 1 to 40 parts by weight with respect to 100 parts by weight of the (A) matrix resin. When the content of the (F) flame retardant is 1 part by weight or more, a flame retardant effect can be obtained, and when it is 40 parts by weight or less, the decrease in mechanical strength and heat resistance is small.

[0075] Examples of the method for adding the (F) flame retardant include a method of blending the (F) flame retardant into the dispersed phase resin and the continuous phase resin in the resin composition, respectively. Specifically, a method of blending one or more flame retardants selected from the group consisting of phosphate esters, nitrogen-containing cyclic compounds, nitrogen-containing phosphate compounds, phosphazene compounds, boric acid compounds, silicone oils, and phosphinates into the resin forming the dispersed phase and the resin forming the continuous phase can be mentioned.

[0076] Among them, it is preferable to blend different flame retardants into the dispersed phase and the continuous phase, respectively. Specifically, it is preferable to blend one or more selected from the group consisting of phosphate esters, nitrogen-containing phosphate compounds, phosphazene compounds, and silicone oils into the dispersed phase, and blend one or more selected from the group consisting of nitrogen-containing cyclic compounds, nitrogen-containing phosphate compounds, boric acid compounds, and phosphinates into the continuous phase.

[0077] (Dripping inhibitor) Moreover, the thermoplastic resin composition may further contain a dripping inhibitor. Examples of the dripping inhibitor include fluorine-based polymers such as tetrafluoroethylene. In addition, the content of the dripping inhibitor is preferably an amount such that the halogen concentration is less than 2% by mass when the total amount of the thermoplastic resin composition is 100% by mass. In this case, the dripping inhibitor also acts as a flame retardant.

[0078] (Colorant) Further, the thermoplastic resin composition may further contain a colorant. There is no particular limitation on the method of coloring the thermoplastic resin composition, and one or more colorants selected from known organic dyes and pigments and inorganic pigments can be used. Examples of organic dyes and pigments include azo-based pigments such as azo lake pigments, benzimidazolone pigments, diarylide pigments, and condensed azo pigments; phthalocyanine-based pigments such as phthalocyanine blue and phthalocyanine green; condensed polycyclic pigments such as isoindolinone pigments, quinophthalone pigments, quinacridone pigments, perylene pigments, anthraquinone pigments, perinone pigments, and dioxazine violet; azine-based pigments; and carbon black.

[0079] Among these, as carbon black, the dibutyl phthalate (DBP) absorption amount is less than 250 mL / 100 g, preferably less than 150 mL / 100 g, and the nitrogen adsorption specific surface area is less than 900 m 2 / g, more preferably less than 400 m 2 / g. When these are within this range, a composition particularly excellent in colorability, mechanical strength, and flame retardancy can be obtained.

[0080] The DBP absorption amount and the nitrogen adsorption specific surface area referred to here are the values measured by the methods defined in ASTM D2414 and JIS K6217, respectively. Examples of azine-based dyes include Solvent Black 5 (C.I. 50415, CAS No. 11099-03-9), Solvent Black 7 (C.I. 50415:1, CAS No. 8005-20-5 / 101357-15-7), and Acid Black 2 (C.I. 50420, CAS No. 8005-03-6 / 68510-98-5) in the Color Index.

[0081] Examples of inorganic pigments include metal oxides excluding iron oxides such as zinc oxide and chromium oxide, and composite metal oxides such as titanium yellow, cobalt blue, and ultramarine blue. When the total amount of the resin composition is 100% by mass, the preferable addition amount of the colorant is 2% by mass or less for carbon black, 2% by mass or less for azo dyes, and 8% by mass or less for inorganic pigments. More preferable amounts are 1% by mass or less for carbon black, 1% by mass or less for azo dyes, and 5% by mass or less for inorganic pigments. By adding in the above addition amounts, the balance of impact resistance and mechanical properties can be maintained well. Also, in the case of applications where flame retardancy is required, the above addition amounts are preferable from the viewpoint of flame retardancy.

[0082] (Inorganic filler) In addition to the above-described components, the thermoplastic resin composition can add an inorganic filler at an arbitrary stage as necessary within a range that does not impair the effects of the present embodiment.

[0083] Examples of the inorganic filler include fibrous, granular, plate-like, or needle-like inorganic reinforcing materials such as glass fiber, potassium titanate fiber, gypsum fiber, brass fiber, ceramic fiber, boron whisker fiber, mica, talc, silica, calcium carbonate, kaolin, calcined kaolin, wollastonite, zonoite, apatite, glass beads, glass flakes, and titanium oxide. These inorganic fillers can be used in combination of two or more. Among these, more preferable inorganic fillers include glass fiber, carbon fiber, and glass beads. Also, the inorganic filler may be a surface-treated product surface-treated by a known method using a surface treatment agent such as a silane coupling agent. However, since natural ore-based fillers often contain a trace amount of iron element, it is necessary to select and use a purified product excluding the iron element.

[0084] When the total amount of the thermoplastic resin composition is 100% by mass, the specific preferable addition amount of each of the inorganic fillers is 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less. In addition, when the total amount of the thermoplastic resin composition is 100% by mass, the preferable addition amount of the total inorganic filler is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less.

[0085] The inorganic filler may be surface-treated, and known ones can be used. Fibrous fillers and plate-like fillers are preferred. Examples of the fibrous filler include, but are not limited to, glass fiber, carbon fiber, whiskers such as potassium titanate whisker, and calcium silicate (wollastonite). Examples of the plate-like filler include, but are not limited to, glass flakes, mica, talc, and the like. These may be used alone or in combination of two or more. Among these fillers, glass fiber is most preferred from the viewpoints of rigidity and water resistance.

[0086] The surface treatment of the inorganic filler is not particularly limited. For example, surface treatment using various coupling agents such as silane-based and titanate-based coupling agents can be mentioned. In particular, from the viewpoint of enhancing the adhesion between the resin and the surface-treated inorganic filler and improving the vibration fatigue characteristics and impact resistance of the resin composition, surface treatment using a silane-based coupling agent such as aminosilane or epoxy silane is preferred. In addition, it is preferable from the viewpoint of water resistance to include it in a surface treatment agent containing an acid functional group.

[0087] It should be noted that whether the acid functional group is included can be determined by extracting the surface treatment agent of glass fiber in chloroform and measuring it by PyGCMS to see if a peak derived from an acid is detected. In particular, it is preferable from the viewpoint of water resistance to use glass fiber in which a peak derived from carboxylic acid is detected.

[0088] Examples of the acid that constitutes the compound containing the acid functional group, and unsaturated carboxylic acids and their derivatives include unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, acrylic acid, tetrahydrophthalic acid, citraconic acid, crotonic acid, and isocrotonic acid. Examples of their derivatives include, for example, anhydrides, acid halides, amides, imides, esters, etc. Specifically, maleic anhydride, acetic anhydride, succinic anhydride, monomethyl maleate, dimethyl maleate, maleimide, glycidyl maleate, etc. are exemplified.

[0089] The silane-based coupling agent (silane coupling agent) used for the surface treatment is not particularly limited, but preferably 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane.

[0090] Examples of the method for surface treatment of the inorganic filler include, for example, when the inorganic filler is glass fiber, when the fibrous inorganic filler is spun and converged, a silane coupling agent is applied to the surface together with a sizing agent and then dried. When the inorganic filler is in the form of short fibers or powder, methods such as impregnating these fillers with a silane coupling agent solution and then drying can be mentioned. Here, the temperature during drying is preferably 100 °C or higher.

[0091] As the glass fiber, fibers obtained by melt spinning generally supplied E glass (Electrical glass), C glass (Chemical glass), A glass (Alkali glass), S glass (High strength glass), D glass, R glass, and alkali-resistant glass, etc. are used. A preferred example of this embodiment is E glass, and D glass is also preferred in order to achieve lower dielectric.

[0092] In order to further lower the dielectric properties of the resin composition, the inorganic fiber is preferably an inorganic fiber with low dielectric properties, and more preferably a glass fiber with low dielectric properties. The low-dielectric inorganic fiber means an inorganic fiber with a low relative permittivity and a low dielectric loss tangent. For example, inorganic fibers with a relative permittivity of 7 or less are exemplified. The relative permittivity here is a value measured according to ASTM D 150. Examples of such low-dielectric glass fibers include, for example, 65 to 85% by mass of SiO 2 and 15 to 30% by mass of B 2 O 3 and 0 to 4% by mass of sodium oxide (Na 2 O) and / or potassium oxide (K 2 O), and glass fibers composed of 0 to 4% by mass of other components (the total amount here does not exceed 100% by mass, and preferably the total is 100% by mass). Glass fibers with a large amount of B 2 O 3 are known as glass fibers with a low relative permittivity.

[0093] The thermoplastic resin composition may further contain 0.1 to 300.0 parts by mass of talc based on 100 parts by mass of the laser direct structuring additive. By containing talc, dimensional stability and product appearance can be improved, and the plating growth rate can be increased. Furthermore, by containing talc, the plating property of the resin molded product can be improved even if the content of the LDS additive is reduced. As the talc, those surface-treated with at least one compound selected from polyorganohydrogensiloxanes and organopolysiloxanes may be used. In this case, the adhesion amount of the siloxane compound in the talc is preferably 0.1 to 5% by mass of the talc.

[0094] The number average particle diameter of the talc is preferably from 0.1 to 50 μm, more preferably from 0.1 to 25 μm. Talc is usually scaly, and the length of the longest part is taken as the average particle diameter. The number average particle diameter of talc is calculated from the measured values obtained by randomly extracting the talc whose particle diameter is to be measured from the image obtained by observation with an electron microscope and measuring the particle diameter. The magnification of the observation is 1,000 times, and the number of measurements is 1,000 or more.

[0095] Incidentally, the thermoplastic resin composition may contain only one kind of talc or may contain two or more kinds of talc.

[0096] In the parts for communication equipment of this embodiment, materials with a low dielectric constant are often preferably used. However, for miniaturization, control of the dielectric constant is required, and materials with a high dielectric constant may be required. In that case, the dielectric constant can be controlled by adding an inorganic filler with a high dielectric constant. For example, titanium oxide, calcium carbonate, etc. can be cited as examples. Even when a high dielectric constant is required, it is preferable to keep the dielectric tangent low, and materials whose dielectric tangent increases due to water absorption, etc. deteriorate the performance as an antenna.

[0097] (Other components) Incidentally, the thermoplastic resin composition may contain, in addition to the above-described components, as other additive components, plasticizers (such as low molecular weight polyolefins, polyethylene glycols, fatty acid esters, etc.), antistatic agents, nucleating agents, fluidity improvers, reinforcing agents, various peroxides, spreading agents, copper-based heat stabilizers, organic heat stabilizers typified by hindered phenol-based oxidation inhibitors, antioxidants, ultraviolet absorbers, light stabilizers, lubricants such as ethylene bisstearic acid amide, and modifying agents such as maleic anhydride.

[0098] When the total amount of the thermoplastic resin composition is 100% by mass, the specific preferable addition amounts of the other components are each 15% by mass or less, more preferably 13% by mass or less, and still more preferably 10% by mass or less. Also, as the preferable addition amount of the whole of the other components, when the whole of the thermoplastic resin composition is taken as 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.

[0099] (Method for producing thermoplastic resin composition) The thermoplastic resin composition can be produced by melt-kneading each component constituting the (A) matrix resin, the (B) LDS additive, and further, a colorant, an inorganic filler, and other components as necessary.

[0100] The melt-kneading machine for performing melt-kneading is not limited to the following, and examples thereof include heating melt-kneading machines such as a single-screw extruder, a multi-screw extruder including a twin-screw extruder, a roll, a kneader, a Brabender plastograph, and a Banbury mixer. In particular, from the viewpoint of kneading property, a twin-screw extruder is preferable. Specifically, the ZSK series manufactured by WERNER&PFLEIDERER, the TEM series manufactured by Toshiba Machine Co., Ltd., the TEX series manufactured by Nippon Steel & Sumitomo Metal Corporation, etc. can be mentioned.

[0101] The melt-kneading temperature at this time can be selected as a temperature at which heating and melting can be performed without difficulty at a temperature equal to or higher than the melting point temperature of the crystalline resin in the case of a crystalline resin, or equal to or higher than the glass transition temperature of the non-crystalline resin, and can usually be arbitrarily selected from 200 to 370°C. In particular, it is preferable to process at a processing temperature of 260°C or higher, and the interparticle distance can be controllably adjusted by achieving a viscosity of a certain level or higher.

[0102] A preferable production method using an extruder is described below. The L / D (barrel effective length / barrel inner diameter) of the extruder is preferably 20 or more and 60 or less, more preferably 30 or more and 50 or less. The configuration of the extruder is not particularly limited. For example, in the raw material flow direction, a first raw material supply port is provided on the upstream side, a first vacuum vent is provided downstream of the first raw material supply port, and a second raw material supply port is provided downstream of the first vacuum vent (if necessary, a third and a fourth raw material supply port may be further provided downstream of the second raw material supply port). Further, it is preferable that a second vacuum vent is provided downstream of the second raw material supply port. When using a liquid addition pump, it is more preferable from the viewpoint of developing flame retardancy that a liquid addition pump is provided downstream of the second raw material supply port and a second vacuum vent is provided downstream of the liquid addition pump. Further, the method of supplying the raw material at the second, third, and fourth raw material supply ports is not particularly limited, and it may be a method of simply adding from the upper opening of the raw material supply port or a method of adding using a forced side feeder from the side opening. In particular, from the viewpoint of stable supply, a method of adding using a forced side feeder from the side opening is preferable. In particular, it is more preferable that a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the first vacuum vent and the second raw material supply port, and a kneading section is provided between the second to fourth raw material supply ports and the second vacuum vent.

[0103] Furthermore, the configuration of the screw provided in the barrel is not particularly limited, and it may be configured to appropriately provide right-handed, left-handed, orthogonal (N-type), and reverse-feed (L-type) kneading disk elements. In particular, between the first raw material supply port and the second raw material supply port, at least one orthogonal (N-type) kneading disk element and at least one reverse-feed (L-type) kneading disk element are provided, and between the liquid addition pump and the vacuum vent downstream of the liquid addition pump, a configuration in which at least one orthogonal (N-type) kneading disk element is provided is preferable because the dispersion state of the (B) LDS additive can be controlled within a specific range. In particular, those including one or more reverse screws are preferable because they can control the inter-particle distance. However, if there are too many reverse screws, excessive kneading will occur, which is not preferable. The number of reverse screws is preferably 2 or more and 5 or less. The reverse screw may have any shape such as reverse feed or reverse kneading, but refers to a screw in the direction opposite to the feed direction.

[0104] When adding a liquid raw material, it can be added by directly feeding the liquid raw material into the cylinder system using a liquid addition pump or the like in the extruder cylinder part. The liquid addition pump is not particularly limited, and examples include a gear pump and a flange-type pump, and a gear pump is preferable. At this time, from the viewpoint of reducing the load on the liquid addition pump and improving the operability of the raw material, it is preferable to heat the part that becomes the flow path of the liquid raw material, such as the tank for storing the liquid raw material, the pipe between the tank and the liquid addition pump, and the pipe between the pump and the extruder cylinder, using a heater or the like to reduce the viscosity of the liquid raw material.

[0105] The method for supplying the raw materials to the second to fourth raw material supply ports is not particularly limited, but the method of supplying using a forced side feeder from the side opening of the extruder is more preferable because it tends to be able to supply more stably than simply adding and supplying from the opening of the second to fourth raw material supply ports of the extruder.

[0106] In particular, when the raw material contains powder and it is desired to reduce the generation of cross-linked products and carbides due to the thermal history of the resin, a method using a forced side feeder supplied from the extruder side is more preferable. It is even more preferable to provide a forced side feeder at the second to fourth raw material supply ports and divide and supply the powder of these raw materials. In particular, it is preferable to provide the (B) LDS additive at the second to fourth raw material supply ports to enable control of the interparticle distance. When adding a liquid raw material, a method of adding it into the extruder using a plunger pump, a gear pump, or the like is preferable.

[0107] The upper openings of the second to fourth raw material supply ports of the extruder can also be used as openings for venting the conveyed air.

[0108] Regarding the melt-kneading temperature and screw rotation speed in the melt-kneading process of the thermoplastic resin composition, there are no particular limitations. However, in the case of a crystalline resin, a temperature above the melting point temperature of the crystalline resin can be selected, and in the case of an amorphous resin, a temperature above its glass transition temperature can be selected so that it can be heated and melted and processed without difficulty. Usually, it can be arbitrarily selected from 200 to 370 °C, and the screw rotation speed can be set to 100 to 1200 rpm.

[0109] As one specific manufacturing method aspect of the thermoplastic resin composition using a twin-screw extruder, for example, each component constituting the (A) component and the raw material titanium dioxide are supplied to the first raw material supply port of the twin-screw extruder, the heating and melting zone is set to the melting temperature of the thermoplastic resin, and melt-kneading is performed at a screw rotation speed of 100 to 1200 rpm, preferably 200 to 500 rpm. Also, the position where each component constituting the (A) component and the raw material titanium dioxide are supplied to the twin-screw extruder may be supplied all at once from the first raw material supply port of the extruder as described above, or the second raw material supply port, the third raw material supply port, and the fourth raw material supply port may be provided and each component may be supplied separately. Furthermore, when reducing the generation of crosslinked products and carbides due to the thermal history of the resin in the presence of oxygen, it is preferable to maintain the oxygen concentration of each individual process line in the addition path of each raw material to the extruder at less than 1.0% by volume. The addition path is not particularly limited, but specific examples may include a configuration such as, in order from the stock tank, piping, a gravimetric feeder equipped with a refill tank, piping, a supply hopper, and a twin-screw extruder. As a method for maintaining such a low oxygen concentration, although not particularly limited, a method of introducing an inert gas into each individual process line with enhanced airtightness is effective. Usually, it is preferable to introduce nitrogen gas to maintain the oxygen concentration at less than 1.0% by volume.

[0110] When the thermoplastic resin in component (A) of the resin composition described above contains a powdery component (volume average particle diameter less than 10 μm), when manufacturing the resin composition using a twin-screw extruder, it has the effect of further reducing the residue in the screw of the twin-screw extruder, and furthermore, in the resin composition obtained by the manufacturing method described above, it has the effect of reducing the generation of black dot foreign matters, carbides, etc.

[0111] As a specific manufacturing method of the thermoplastic resin composition, it is preferable to use an extruder with the oxygen concentration of each raw material supply port controlled to less than 1.0% by volume and implement any one of the following methods 1 to 2. 1. A manufacturing method including a step of melt-kneading a part constituting component (A) contained in the resin composition of the present embodiment (first kneading step), and supplying the entire amount of the (B) LDS additive to the kneaded product in the molten state obtained in the first kneading step, and then continuously performing melt-kneading (second kneading step). 2. A manufacturing method including a step of melt-kneading a part constituting component (A) contained in the resin composition of the present embodiment (first kneading step), supplying a part of the (B) LDS additive to the kneaded product in the molten state obtained in the first kneading step and performing melt-kneading (second kneading step), and supplying the remaining amount of the (B) LDS additive and then continuously performing melt-kneading (third kneading step).

[0112] 〔Properties of Thermoplastic Resin Composition〕 Hereinafter, the properties of the resin molded body made of the resin composition will be described. As the Vicat softening temperature (°C) of the thermoplastic resin composition constituting the communication device parts of the present embodiment, a larger value indicates an improvement in heat resistance and is preferable.

[0113] The Vicat softening temperature refers to the value measured by the method described in the examples below. Antenna parts for high frequencies generate a large amount of heat, and the higher the frequency, the greater the heat generation, and thus they are required to have high heat resistance. In particular, this is required for antenna parts with a frequency of 1 GHz or higher. From such a viewpoint, it is necessary to have a Vicat softening temperature of 90°C or higher. The Vicat softening temperature is preferably 90°C or higher, more preferably 95°C or higher. The higher the Vicat softening temperature, the more preferable. Also, from the viewpoint of enabling melt kneading during production, it is preferable that the Vicat softening temperature is not too high, preferably 350°C or lower, more preferably 330°C or lower, and even more preferably 315°C or lower. The Vicat softening temperature is measured based on JIS K 7206 and can be measured, for example, by the method described in the examples below.

[0114] Also, as the heat deflection temperature under load (DTUL) (°C) of the thermoplastic resin composition, a higher value indicates an improvement in heat resistance and is preferable. The heat deflection temperature under load (DTUL) refers to the value measured by the method described in the examples below.

[0115] Antenna parts for high frequencies generate a large amount of heat, and the higher the frequency, the greater the heat generation, and thus a resin with high heat resistance is required. Particularly for antenna components with frequencies of 1 GHz or higher, it is preferably a resin molded body made of a resin composition having a DTUL of 90°C or higher, more preferably 92°C or higher, and even more preferably 95°C or higher. The higher the heat resistance, the better. Also, from the perspective of enabling melt kneading during manufacturing, the DTUL is preferably not too high, preferably 370°C or lower, more preferably 350°C or lower, and even more preferably 330°C or lower.

[0116] In the component for a communication device of this embodiment, the water absorption rate of the thermoplastic resin composition is 1.5% or less. Generally, components for communication devices such as antennas are often used in an open state, and when the water absorption is high, they will absorb moisture in the air. Generally, when water is absorbed, the deterioration of the dielectric constant described later occurs, and from the perspective that the antenna performance is significantly reduced, the water absorption rate needs to be 1.5% or less, preferably 1.0% or less, and more preferably 0.5% or less. The water absorption rate preferably has a smaller value. Note that the water absorption rate is measured based on JIS K 7209 and can be measured, for example, by the method described in the examples below.

[0117] For the resin molded body (thermoplastic resin composition) constituting the component for a communication device of this embodiment, a smaller value of the dielectric constant indicates an improvement in antenna performance and is preferable. The dielectric constant of the resin molded body (thermoplastic resin composition) is preferably 3.0 or less, more preferably 2.9 or less, and even more preferably 2.8 or less. Note that the dielectric constant refers to the value measured by the method described in the examples below.

[0118] The dielectric tangent of the resin molded body made of the above thermoplastic resin composition preferably has a smaller value, indicating a reduction in the energy loss rate. In particular, the dielectric tangent is a parameter for which water absorption is a concern, and a thermoplastic resin composition in which the dielectric tangent does not increase after immersion in warm water at 80 °C for 144 hours is preferred as an index showing the characteristics after long-term water absorption. It can be said that a material with a lower dielectric tangent after immersion is less likely to absorb water over a long period. The dielectric tangent of the resin molded body (thermoplastic resin composition) is preferably 0.008 or less, more preferably 0.007 or less, and even more preferably 0.006 or less.

[0119] Note that the dielectric tangent refers to the value measured by the method described in the examples below.

[0120] 〔Molded Body, Parts for Communication Equipment〕 The resin molded body constituting the parts for communication equipment of the present embodiment is made of the above-described thermoplastic resin composition. The manufacturing method of the resin molded body is not particularly limited, but it can be manufactured, for example, by injection molding. Also, it can be used in a form in which a coating layer made of paint, metal, or other types of polymers is formed on the surface of the molded body manufactured by such a method. The parts for communication equipment of the present embodiment include one or more of the above-described molded bodies. The parts for communication equipment may have a structure in which a plurality of molded bodies are fitted together.

[0121] The parts for communication equipment of the present embodiment have a conductive part on the surface of the resin molded body. The conductive part has conductivity and can be formed by applying metal ink or plating. The conductive part can have one or more selected from the group consisting of a metal circuit, a metal wiring, and a metal substrate. And, in the parts for communication equipment of the present embodiment, the conductive part is formed by laser direct structuring (LDS). LDS can be performed, for example, as shown in FIGS. 1 and 2 as described above. Particularly after this laser irradiation, annealing treatment can be performed at 80°C for 24 hours, and then, by cleaning with ultrasonic treatment, it can be adjusted to an appropriate surface roughness. The surface roughness refers to the value measured by the method described in the examples below. By increasing the ultrasonic cleaning time instead of the annealing treatment, it is also possible to adjust to an appropriate surface roughness. Alternatively, by adjusting the output of the laser, it is also possible to adjust to an appropriate surface roughness. Furthermore, it is also possible to adjust the surface roughness by increasing the thickness of the plating. The thicker the plating thickness, the smoother the surface becomes. However, from the perspective of productivity, the plating thickness is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less. Also, if the surface is too smooth, it is difficult to exhibit the adhesion between the plating and the resin. From this perspective, the surface roughness Sa is preferably 0.5 μm to 30 μm, more preferably 0.6 to 28 μm, and even more preferably 0.7 to 28 μm. Thermoplastic resins are easier to adjust the surface roughness by adjusting the conditions. For example, in the case of thermosetting resins, although the surface roughness Ra in terms of lines can be adjusted by adjusting the conditions, it is difficult to adjust the surface roughness Sa in terms of surfaces and it is difficult to exhibit the characteristics.

[0122] In addition, the type of plating applied to the resin molded body is not particularly limited, and it can be used regardless of whether it is gold, silver, or copper. Furthermore, those containing a plurality of metals can also be used. In addition, any metal can be used for the metal ink. Furthermore, in this embodiment, the antenna performance can be exhibited even at high temperatures. Antenna components are often used in high-temperature environments, and maintaining the antenna performance at high temperatures is highly regarded.

[0123] One of the features of the component for a communication device of this embodiment is that it has high copper corrosion prevention properties and can reduce cracking after the application of the metal ink or plating. Also, the laser used is not particularly defined, and it can be appropriately selected from known lasers such as YAG lasers, excimer lasers, and electromagnetic rays. Also, the wavelength of the laser is not particularly defined.

[0124] When the resin molded body is irradiated with a laser, only the irradiated portion is activated. In this activated state, the resin molded body is brought into contact with a plating solution. The plating solution is not particularly defined, and known plating solutions can be widely adopted. As the metal component, a plating solution composed of one or more of copper, nickel, silver, gold, and palladium (particularly, an electroless plating solution) is preferable, a plating solution composed of one or more of copper, nickel, silver, and gold (particularly, an electroless plating solution) is more preferable, and a plating solution containing copper (particularly, an electroless plating solution) is even more preferable. That is, in the plating, it is preferable that the metal component is composed of at least one of the metals.

[0125] In the method for forming a component for a communication device according to the present embodiment, a plating (circuit) having an interval with a width of 1 mm or less, and further 150 μm or less (the lower limit value is not particularly defined, for example, 30 μm or more) can be formed. In order to suppress corrosion and deterioration of the formed plating (circuit), for example, after performing electroless plating, it can be further protected with nickel and gold. Similarly, electrolytic plating can be used after electroless plating to form a required film thickness in a short time.

[0126] In addition, when applying a metal ink to the surface of the resin molded body, there are various methods for adhering it to the resin. A method that requires heat resistance, such as a method of adhering using a laser, can also be used for the component for a communication device according to the present embodiment.

[0127] For example, in a component for a communication device, by using an inkjet method, a circuit pattern of a wiring board can be drawn and formed with a conductive metal paste. This method for forming a circuit pattern may be according to a known method (see, for example, JP-A-2002-324966). The conductive metal paste to be used is a conductive metal paste in which metal ultrafine particles with a fine average particle diameter are uniformly dispersed in a thermosetting resin composition containing an organic solvent. The metal ultrafine particles with this fine average particle diameter are selected such that their average particle diameter is in the range of 1 to 100 nm, and the surface of the metal ultrafine particles is preferably coated with one or more compounds having a group containing nitrogen, oxygen, or sulfur atoms as a group capable of coordinatively bonding with the metal element contained in such metal ultrafine particles.

[0128] The metal ultrafine particles with a fine average particle diameter contained in the conductive metal paste are preferably fine particles composed of one type of metal selected from the group consisting of gold, silver, copper, platinum, palladium, tungsten, nickel, tantalum, bismuth, lead, indium, tin, zinc, titanium, and aluminum, or fine particles of an alloy composed of two or more types of metal.

[0129] The method for forming a circuit pattern includes a step of ejecting and applying the conductive metal paste as minute droplets onto a substrate to draw a circuit pattern composed of a coating film of the conductive metal paste, and a step of heat-treating the drawn coating film of the conductive metal paste at least at a temperature at which the thermosetting of the thermosetting resin is performed.

[0130] As the drawing means by an inkjet method, there are a thermal drawing means that generates bubbles by heat foaming and discharges droplets, and a piezo drawing means that discharges droplets by compression using a piezo element.

[0131] The parts for communication equipment of this embodiment can be used for various applications such as electronic parts such as sensors, connectors, switches, relays, conductive circuits, and antennas (particularly, parts for portable electronic devices, communication base stations, and peripheral devices for personal computers).

Examples

[0132] Hereinafter, the present embodiment will be described in more detail by way of examples and comparative examples, but the present embodiment is not limited to these examples.

[0133] The raw materials used in the examples and comparative examples are shown below. [Raw materials] (A-a) Polyphenylene ether (A-a-1) Polyphenylene ether resin obtained by oxidative polymerization of 2,6-xylenol The reduced viscosity (measured at 0.5 g / dL, chloroform solution, 30 °C) of the polyphenylene ether resin (A-a-1) was 0.52 dL / g. (A-a-2) Polyphenylene ether resin obtained by oxidative polymerization of 2,6-xylenol The reduced viscosity (measured at 0.5 g / dL, chloroform solution, 30 °C) of the polyphenylene ether resin (A-a-2) was 0.40 dL / g. (A-a-3) Polyphenylene ether resin obtained by oxidative polymerization of 2,6-xylenol (A-a-2) The reduced viscosity (measured at 0.5 g / dL, chloroform solution, 30 °C) of the polyphenylene ether resin (A-a-3) was 0.32 dL / g.

[0134] (B) LDS additive (B-1) Antimony-doped tin oxide (manufactured by Keeling & Walker Limited, trade name "StanoStat CP05") (B-2) Copper chromic acid (manufactured by Shepherd Color, trade name "LD14")

[0135] (A-b) A block copolymer containing at least one block mainly composed of an aromatic vinyl monomer unit and at least one block mainly composed of a conjugated diene monomer unit, and / or a hydrogenated product of the block copolymer Hydrogenated block copolymer (manufactured by Asahi Kasei Corporation, trade name "Taftec (registered trademark) H1051")

[0136] (A-c) Polystyrene-based resin (A-c-1) Polystyrene (manufactured by PS Japan Corporation, trade name "GPPS685") (A-c-2) High-impact polystyrene (product name "CT-60" manufactured by petrochemicals)

[0137] (A-d) Polyamide 6,6 (hereinafter referred to as PA66) 2400 g of an equimolar salt of adipic acid and hexamethylenediamine, 100 g of adipic acid, and 2.5 liters of pure water were charged into a 5-liter autoclave and stirred well. After thoroughly replacing the atmosphere in the autoclave with nitrogen, the temperature was raised from room temperature to 220 °C over about 1 hour while stirring. At this time, the gauge pressure in the autoclave became 1.76 MPa due to the natural pressure of steam. Subsequently, heating was continued while removing water outside the reaction system so that the pressure did not exceed 1.76 MPa. After another 2 hours, when the internal temperature reached 260 °C, while continuing heating, the pressure was reduced to 0.2 MPa over about 40 minutes by opening and closing the valve of the autoclave. Then, it was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 2 kg of polymer was taken out and pulverized. The obtained polyamide had Mw = 38700 and Mw / Mn = 2.1. Here, Mw and Mn were determined using GPC (mobile phase: hexafluoroisopropanol, standard substance: PMMA (polymethyl methacrylate)). Also, as a result of measurement according to the method for measuring the terminal amino group concentration described in the examples of JP-A-7-228689, the terminal amino group concentration was 38 μmol / g.

[0138] (A-e) Polypropylene homopolymer with MFR = 2 g / 10 min

[0139] (A-f) Polyethylene resin (A-f-1) High-density polyethylene resin ("Suntech-HD B161" manufactured by Asahi Kasei Corporation) (A-f-2) High-density polyethylene resin ("Suntech-HD J320" manufactured by Asahi Kasei Corporation)

[0140] (C~E) Other components (C) Ethylene bisstearamide: "Kaowax EB-G" manufactured by Kao Corporation (D) Maleic anhydride (manufactured by NOF Corporation, "Crystal MAN") (E) Calcium carbonate (SL-2200 manufactured by Takehara Chemical Industry Co., Ltd.)

[0141] (MF) Inorganic filler (MF-1) Glass fiber (ECS03-T249 manufactured by Nippon Electric Glass Co., Ltd.) (MF-2) Glass flake (MEG160FY M06 manufactured by Nippon Sheet Glass Co., Ltd.) (MF-3) Talc (Crown Talc PK-MMB manufactured by Matsumura Sangyo Co., Ltd.)

[0142] (FR) Flame retardant (FR-1) Product name E890 manufactured by Daihachi Chemical Industry Co., Ltd. (FR-2) Product name PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.

[0143] [Examples 1 to 18, Comparative Examples 1 to 10] The components were blended with the compositions shown in Tables 1 and 2, and a resin composition was produced using a twin-screw extruder ZSK-40 (manufactured by COPERION WERNER & PFLEIDERER, Germany). In this twin-screw extruder, a first raw material supply port was provided upstream in the flow direction of the raw materials, a first vacuum vent was provided downstream of this, a second raw material supply port was provided downstream of that, a third raw material supply port was provided downstream of that, and a second vacuum vent was provided further downstream. Also, as necessary, additional liquid addition pumps and vacuum vents were provided downstream of the first raw material supply port, and their positions were appropriately changed as necessary. Here, four kneading sections were provided (one between the first supply port and the first vacuum vent, one between the first vacuum vent and the second supply port, one between the second supply port and the third supply port, and one between the third supply port and the second vacuum vent). Reverse feed (L-type) kneading disk elements in the number described in the table were arranged in these four kneading sections. Using the extruder set as described above, each component was added with the compositions and addition methods shown in Tables 1 and 2, and melt-kneaded under the conditions of an extrusion temperature of 250 to 320 °C, a screw rotation speed of 300 rpm, and a discharge rate of 100 kg / hour to produce pellets.

[0144] [Evaluation Method] Using the resin compositions obtained in the examples and comparative examples, the following evaluations were conducted. The evaluation results are shown in Tables 1 and 2. (1) Dielectric Constant and Dielectric Loss Tangent The pellets of the obtained resin composition were supplied to a small injection molding machine (trade name: EC75-SXII, manufactured by Toshiba Machine Co., Ltd.) with the cylinder temperature set at 250 - 290 °C, and a flat plate of 60 mm × 60 mm × 0.9 mm was produced under the conditions of mold temperature 70 - 130 °C, injection pressure 200 MPa, injection time 10 seconds, and cooling time 20 seconds. The dielectric constant and dielectric loss tangent at 2.5 GHz were measured under the following conditions. Measurement Frequency: 2.5 GHz Measuring Device: 10 MHz to 43.5 GHz PNA network analyzer N5224B, 10 GHz Split Post Dielectric Resonator N1501AE10 Measurement Environmental Conditions: Room temperature 23 °C, humidity 50%

[0145] (2) Dielectric Loss Tangent during Water Absorption The pellets of the obtained resin composition were supplied to a small injection molding machine (trade name: EC75-SXII, manufactured by Toshiba Machine Co., Ltd.) with the cylinder temperature set at 340 °C, and a flat plate of 60 mm × 60 mm × 0.9 mm was produced under the conditions of mold temperature 70 - 130 °C, injection pressure 200 MPa, injection time 20 seconds, and cooling time 20 seconds. After immersing in warm water at 80 °C for 144 hours, the dielectric loss tangent at 2.5 GHz was measured under the same conditions as (1).

[0146] (3) Heat Resistance (3-1) Vicat Softening Temperature The pellets of the obtained resin composition were supplied to a small injection molding machine (trade name: EC75-SXII, manufactured by Toshiba Machine Co., Ltd.) with the cylinder temperature set at 340 °C, and a flat plate of 60 mm × 60 mm × 0.9 mm was produced under the conditions of mold temperature 70 - 130 °C, injection pressure 200 MPa, injection time 10 seconds, and cooling time 20 seconds. Using the test pieces cut to an arbitrary size, the test load: 50 N, indenter tip shape: cylindrical cross-sectional area 1 mm 2 , was measured under the conditions of heating rate 50 °C / hr and measurement number n = 2. As an evaluation criterion, it was determined that the higher the Vicat softening temperature, the better the heat resistance and the more advantageous in terms of material design for this application. (3-2) Heat deflection temperature (DTUL) The pellets of the obtained resin composition were supplied to a small injection molding machine (trade name: EC75-SXII, manufactured by Toshiba Machine Co., Ltd.) with the cylinder temperature set at 250 to 350 °C, and an ISO dumbbell for evaluation was produced under the conditions of a mold temperature of 70 to 130 °C, an injection pressure of 200 MPa, an injection time of 20 seconds, and a cooling time of 15 seconds. Also, the ISO dumbbell was cut to produce a test piece for measuring the heat deflection temperature (DTUL). Using the test piece for measuring the heat deflection temperature, the heat deflection temperature: DTUL (ISO 75: 1.80 MPa load) was measured. It was determined that the larger the value, the better the heat resistance. (4) Surface smoothness The pellets of the obtained resin composition were supplied to a small injection molding machine (trade name: EC75-SXII, manufactured by Toshiba Machine Co., Ltd.) with the cylinder temperature set at 280 to 320 °C, and a flat plate of 60 mm × 60 mm × 2.0 mm was produced under the conditions of a mold temperature of 80 °C, an injection pressure of 100 MPa, an injection time of 15 seconds, and a cooling time of 20 seconds. The flat plate was activated using a laser irradiation machine (product name "Micro Line 3D16 0", manufactured by LPKF), and then plating was applied at a plating condition of 57 °C / 45 minutes using an electroless copper plating bath (product name "MID copper 100B1", manufactured by McDermid). Whether annealing was performed at 80 °C for 24 hours after laser irradiation was described in the figures of the examples and comparative examples. Thereafter, using a 3D microscope VR-6200 (manufactured by Keyence Corporation), the circuit portion that had been plated was photographed in the texture image mode at a magnification of 25 times, the height measurement mode was set to standard, and the measurement direction of the proof was set to both sides, and the surface roughness Sa was measured. (5) Antenna performance The simulation of the antenna efficiency was performed under the following conditions. · Antenna substrate: 60 × 7 × 1 mm 3 , fully covered with GND, pattern width 1 mm, thickness 25 μm · Copper + Ni plating · Main substrate: 60×130×1 mm 3 , relative permittivity 4.0, dielectric loss 0.020 Thickness 35 μm, conductivity 5.8×10 7 S / m · Simulation device: MW STUDIO by CST It was adjusted so that the reflection coefficient was 6 dB or less in the operating frequency band. The antenna element length and the matching circuit value were adjusted so that the matching was best at 3.5 GHz, and the antenna efficiency at that time was calculated. The shape and dimensions of the antenna used are shown in Figs. 3(a) and (b). Fig. 3(a) shows the overall aspect of the antenna, and Fig. 3(b) shows an enlarged view of the antenna element part. The dielectric properties (relative permittivity and dielectric tangent) of the material were measured by supplying the pellets of the obtained resin composition to a small injection molding machine (trade name: EC75-SXII, manufactured by Toshiba Machine Co., Ltd.) with the cylinder temperature set at 340 °C, and producing a flat plate of 60 mm×60 mm×0.9 mm under the conditions of mold temperature 70~130 °C, injection pressure 200 MPa, injection time 20 seconds, and cooling time 20 seconds, and measuring the dielectric tangent at 5 GHz under the following conditions. · Measurement frequency: 5 GHz · Measuring device: 10 MHz to 43.5 GHz PNA network analyzer N5224B, 5.2 GHz Split Post Dielectric Resonator N1501AE10 · Measurement environmental conditions: room temperature 23 °C, humidity 50% The surface smoothness of the aforementioned material was also input and the simulation was carried out. The closer the value is to 0, the better the antenna performance. Since this simulation does not consider plating properties, the simulation was carried out assuming that it functions as an antenna even if it is a difficult-to-plate material.

[0147] (6) Conduction test at high temperature After heating the test piece obtained when measuring the surface smoothness in an oven at 100 °C for 3 hours, the oven was opened, and within 60 seconds, a conductivity test was performed by pointing to the left and right of the plating circuit using a resistance measuring instrument (Card Hi Tester manufactured by Hioki E.E. Corporation). Those showing a resistance value were evaluated as OK (good) indicating conductivity, and those showing 0 were evaluated as NG (bad). Those that conducted were evaluated as being able to exhibit antenna performance even at high temperatures.

[0148] (7) Water absorption rate The pellets of the obtained resin composition were supplied to a small injection molding machine (trade name: EC75-SXII, manufactured by Toshiba Machine Co., Ltd.) with the cylinder temperature set at 280 to 320 °C, and a flat plate of 60 mm NG 60 mm NG 2.0 mm was produced under the conditions of a mold temperature of 80 °C, an injection pressure of 100 MPa, an injection time of 15 seconds, and a cooling time of 20 seconds. The molded test piece was immersed in pure water at 23 °C for 24 hours within 3 hours, and the degree of weight change was evaluated as the water absorption rate (%). It can be said that a material with a lower water absorption rate is superior. (8) Adhesion The pellets of the obtained resin composition were supplied to a small injection molding machine (trade name: EC75-SXII, manufactured by Toshiba Machine Co., Ltd.) with the cylinder temperature set at 280 to 320 °C, and a flat plate of 60 mm NG 60 mm NG 2.0 mm was produced under the conditions of a mold temperature of 80 °C, an injection pressure of 100 MPa, an injection time of 15 seconds, and a cooling time of 20 seconds. Activation was performed on the flat plate using a laser irradiator (product name "Micro Line 3D16 0", manufactured by LPKF), and then plating was applied at a plating condition of 57 °C / 45 minutes using an electroless copper plating bath (product name "MID copper 100B1", manufactured by McDermid). Whether the plating was applied was judged visually. Then, a thermal shock test was performed at -30 to 80 °C for 40 cycles (1 hour per temperature). Low temperature side: -30 ± 2 °C, 1 hour High temperature side: 80, 100 ± 2 °C, 1 hour ※ Start from the low temperature side After that, a cut with an NG mark was made on the applied plating using a cutter, and the adhesion of the plating was measured when cellophane tape was attached and peeled off. Those for which the plating adhered to the cellophane tape and peeled off were evaluated as having poor adhesion. OK (Good): The plating adhered, and the plating adhesion was good. NG (Defective): The evaluation result was any one of the following: no plating adhered at all, only partial plating adhered, or the plating adhesion was poor.

[0149]

Table 1

Table 2

Industrial Applicability

[0150] The parts for communication equipment of the present invention can be used for various applications such as electronic components such as sensors, connectors, switches, relays, conductive circuits, antennas (particularly, parts for portable electronic devices, communication base stations, and peripheral devices of personal computers). In particular, it can exhibit high characteristics as an antenna even at high temperatures and in humid conditions, and can be preferably used.

Claims

1. A communication device part comprising a conductive molded article including a resin molded article made of a thermoplastic resin composition and a conductive portion formed on a surface of the resin molded article, the thermoplastic resin composition comprises a polyphenylene ether resin and a laser direct structuring (LDS) additive; The thermoplastic resin composition has a Vicat softening temperature of 90° C. or higher and a water absorption rate of 1.5% or lower, The conductive portion has a surface roughness Sa of 0.5 μm or more and 3 μm or less. Parts for communication equipment.

2. The communication device part according to claim 1 , wherein the conductive portion is formed by laser direct structuring.

3. The LDS additive is (i) copper chromate, or (ii) Compounds containing antimony and tin The communication device part according to claim 1 or 2, comprising:

4. 3. The communication device part according to claim 1 or 2, wherein the thermoplastic resin composition further comprises a block copolymer including at least one block mainly composed of aromatic vinyl monomer units and at least one block mainly composed of conjugated diene monomer units, and / or a hydrogenated product of the block copolymer.

5. The communication device part according to claim 1 or 2, wherein the thermoplastic resin composition has a deflection temperature under load (DTUL) of 90° C. or more.

6. 3. The communication device part according to claim 1, wherein the thermoplastic resin composition has a dielectric constant of 3.0 or less and a dielectric loss tangent of 0.008 or less.

7. 3. The communication device part according to claim 1, wherein the resin molded body has a dielectric loss tangent of 0.03 or less after being immersed in hot water at 80° C. for 144 hours.

8. 3. The communication device part according to claim 1, which is an antenna part.

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