Resin composition, molded article, method for producing molded article with plating, and pellet

Abstract

To provide a resin composition that can serve as a resin composition for LDS, the resin composition being such that, when formed into a molded article, it has superior flame retardancy, maintains a low dielectric loss tangent while attaining a high dielectric constant, and further exhibits a high heat deflection temperature, and also to provide a molded article, a method for producing a molded article with plating, and a pellet.SOLUTION: A resin composition comprising (A) 10 to 90 mass% of a thermoplastic resin, (B) 1 to 20 mass% of a laser direct structuring additive, (C) 1.0 to 7.9 mass% of a phosphorus-based flame retardant, and (D) 0.3 to 7.0 mass% of graphite, where the total of (A) the thermoplastic resin, (B) the laser direct structuring additive, (C) the phosphorus-based flame retardant, and (D) the graphite does not exceed 100 mass%.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a molded article, a method for producing a plated molded article, and pellets. [Background technology]

[0002] In recent years, with the development of mobile phones, including smartphones, various methods for incorporating antennas into mobile phones have been investigated. In particular, there is a demand for methods for incorporating antennas that can be designed in three dimensions into mobile phones. One technology that has attracted attention for forming such three-dimensional antennas is laser direct structuring (hereinafter sometimes referred to as "LDS"). LDS technology is a technology in which, for example, a surface of a resin molded product containing an LDS additive is activated by irradiating it with a laser, and then plating is formed by applying a metal to the activated portion. A feature of this technology is that it allows for the production of metal structures such as antennas directly on the surface of a resin molded product without using adhesives or the like. Such LDS technology is disclosed, for example, in Patent Document 1 and Patent Document 2. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. O2019 / 167854 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-120908 Summary of the Invention [Problem to be solved by the invention]

[0004] Here, resin compositions for laser direct structuring (LDS) are also sometimes required to be flame retardant. Furthermore, for SMT (Surface Mount Technology) applications, they are required to achieve a high dielectric constant while maintaining a low dielectric loss tangent, and also to have a high deflection temperature under load. The present invention aims to solve the above-mentioned problems, and to provide a resin composition that can be used as a resin composition for LDS, and that, when molded into a molded article, has excellent flame retardancy, can achieve a high dielectric constant while maintaining a low dielectric dissipation tangent, and has a high deflection temperature under load, as well as a molded article, a method for manufacturing a plated molded article, and pellets. [Means for solving the problem]

[0005] In light of the above-mentioned problems, the present inventors have conducted research and found that the above-mentioned problems can be solved by using a phosphorus-based flame retardant as the flame retardant in a resin composition containing a thermoplastic resin, a laser direct structuring additive, a flame retardant, and graphite, and adjusting the amount of the phosphorus-based flame retardant. Specifically, the above problems were solved by the following means. <1> A resin composition comprising: (A) 10 to 90 mass% of a thermoplastic resin; (B) 1 to 20 mass% of a laser direct structuring additive; (C) 1.0 to 7.9 mass% of a phosphorus-based flame retardant; and (D) 0.3 to 7.0 mass% of graphite, wherein the total of the (A) thermoplastic resin, (B) laser direct structuring additive, (C) phosphorus-based flame retardant, and (D) graphite does not exceed 100 mass%. <2> The (A) thermoplastic resin includes a polyamide resin. <1> The resin composition according to claim 1. <3> The (A) thermoplastic resin contains a polyamide resin composed of diamine-derived structural units and dicarboxylic acid-derived structural units, and 70 mol % or more of the diamine-derived structural units are derived from xylylenediamine. <1> The resin composition according to claim 1. <4> The (A) thermoplastic resin contains a polyamide resin containing diamine-derived structural units and dicarboxylic acid-derived structural units, in which 70 mol % or more of the diamine-derived structural units are derived from paraxylylenediamine and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from an α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. <1> The resin composition according to claim 1. <5> The (D) graphite is in a flake form. <1> ~ <4> The resin composition according to any one of the above. <6> the mass ratio of the total amount of the laser direct structuring additive (B) and the phosphorus-based flame retardant (C) to the graphite (D) contained in the resin composition, {(C) + (D)} / (B), is less than 1.00; <1> ~ <5> The resin composition according to any one of the above. <7> Furthermore, (E) inorganic reinforcing fibers are contained in a proportion of 60% by mass or less, and the total amount of the (A) thermoplastic resin, (B) laser direct structuring additive, (C) phosphorus-based flame retardant, (D) graphite, and (E) inorganic reinforcing fibers does not exceed 100% by mass. <1> ~ <6> The resin composition according to any one of the above. <8> The (E) inorganic reinforcing fiber includes glass fiber. <7> The resin composition according to claim 1. <9> The (C) phosphorus-based flame retardant contains at least one of a phosphinate and a diphosphinate. <1> ~ <8> The resin composition according to any one of the above. <10> The (C) phosphorus-based flame retardant contains a phosphinate. <1> ~ <9> The resin composition according to any one of the above. <11> The (B) laser direct structuring additive contains copper chromium oxide; <1> ~ <10> The resin composition according to any one of the above. <12> further comprising a nucleating agent, <1> ~ <11> The resin composition according to any one of the above. <13> the (A) thermoplastic resin comprises a polyamide resin containing diamine-derived structural units and dicarboxylic acid-derived structural units, in which 70 mol % or more of the diamine-derived structural units are derived from paraxylylenediamine, and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from an α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms; the (D) graphite is in the form of flakes, the mass ratio of the {(C) phosphorus-based flame retardant + (D) graphite} / (B) laser direct structuring additive is less than 1; Furthermore, the (E) inorganic reinforcing fiber is 60% by mass or less, and the total of the (A) thermoplastic resin, (B) laser direct structuring additive, (C) phosphorus-based flame retardant, (D) graphite, and (E) inorganic reinforcing fiber does not exceed 100% by mass, The (E) inorganic reinforcing fiber contains glass fiber, the (C) phosphorus-based flame retardant contains a phosphinate, the (B) laser direct structuring additive contains copper chromium oxide; The resin composition according to <1>, further comprising a nucleating agent. <14> <1> ~ <13> A molded article formed from the resin composition according to any one of the above items. <15> The surface of the molded article is plated. <14> The molded article according to claim 1. <16> The plating has antenna performance. <15> The molded article according to claim 1. <17> Parts for portable electronic devices, <14> ~ <16> 1. The molded article according to any one of the preceding items. <18> <1> ~ <13> irradiating a surface of a molded article formed from the resin composition according to any one of the above with a laser, and then applying a metal to form a plating. <19> <1> ~ <13> A pellet of the resin composition according to any one of the above. [Effects of the Invention]

[0006] The present invention makes it possible to provide a resin composition that can be used as a resin composition for LDS, and that, when molded into a molded article, has excellent flame retardancy, can achieve a high dielectric constant while maintaining a low dielectric dissipation factor, and has a high deflection temperature under load, as well as a molded article, a method for manufacturing a plated molded article, and pellets. [Brief explanation of the drawings]

[0007] [Figure 1] 1 is a schematic diagram showing a process of plating the surface of a resin molded product. FIG. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, an embodiment for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only this embodiment. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the upper and lower limits. Furthermore, any combination of the upper and lower limit values ​​of the numerical values ​​in this specification is an example of this embodiment. In this specification, various physical properties and characteristic values ​​are those at 23°C unless otherwise specified.

[0009] In this specification, unless otherwise specified, the number average molecular weight is a value measured by the following method. The number average molecular weight (Mn) was measured by gel permeation chromatography (GPC) using a standard polymethyl methacrylate (PMMA) equivalent. Two columns packed with styrene polymer were used as the packing material, and the solvent was hexafluoroisopropanol (HFIP) with a sodium trifluoroacetate concentration of 2 mmol / L. The resin concentration was 0.02% by mass, the column temperature was 40°C, the flow rate was 0.3 mL / min, and measurements were performed using a refractive index detector (RI). A calibration curve was also measured by dissolving six levels of PMMA in HFIP. In this specification, unless otherwise specified, the melting point (Tm) is a value measured by differential scanning calorimetry (DSC) in accordance with ISO 11357. Specifically, it can be measured as described in paragraph 0036 of WO 2016 / 084475, the contents of which are incorporated herein by reference. If the measurement methods, etc. described in the standards shown in this specification change from year to year, they will be based on the standards in effect as of January 1, 2024, unless otherwise specified. If the measurement methods, etc. described in the standards shown in this specification are abolished as of January 1, 2024, they will be based on the standards in effect at the time of abolition. The scale of Figure 1 may not be consistent with reality.

[0010] The resin composition of this embodiment is characterized by comprising 10 to 90 mass% of (A) a thermoplastic resin, 1 to 20 mass% of (B) a laser direct structuring additive (LDS additive), 1.0 to 7.9 mass% of (C) a phosphorus-based flame retardant, and 0.3 to 7.0 mass% of (D) graphite, and the total of the (A) thermoplastic resin, (B) laser direct structuring additive, (C) the phosphorus-based flame retardant, and (D) graphite does not exceed 100 mass%. By configuring in this way, the resin composition can be used as a resin composition for LDS, and when molded into a molded article, a resin composition can be obtained that has excellent flame retardancy, can achieve a high dielectric constant while maintaining a low dielectric dissipation tangent, and further has a high deflection temperature under load. (B) By adding an LDS additive, plating properties can be achieved. Also, by adding a flame retardant, flame resistance can be achieved. (D) By adding graphite, the dielectric constant can be increased. However, if the blending amount of (D) graphite is too large, the dielectric loss tangent tends to be high and plating properties tend to be poor. Furthermore, if a flame retardant is blended, the deflection temperature under load tends to be low. Meanwhile, the inventors have conducted research and found that blending (C) a phosphorus-based flame retardant as a flame retardant can improve plating properties. Under these circumstances, the present inventors have succeeded in obtaining a resin composition that can be used as a resin composition for LDS by precisely adjusting the blending amounts of (B) laser direct structuring additive, (C) phosphorus-based flame retardant, and (D) graphite, and that has excellent flame retardancy, a high dielectric constant while maintaining a low dielectric dissipation factor, and a high deflection temperature under load. The resin composition of this embodiment will be described in detail below.

[0011] <(A) Thermoplastic resin> The resin composition of the present embodiment contains a thermoplastic resin. The thermoplastic resin used in this embodiment is preferably selected from polyamide resin, polycarbonate resin, polyester resin, polyolefin resin, polypropylene resin, styrene-based resin, polyethylene resin, and acrylic resin. Among these, polyamide resin, polycarbonate resin, and styrene-based resin are preferred, polyamide resin and polycarbonate resin are more preferred, and polyamide resin is even more preferred.

[0012] <<Polyamide resin>> Polyamide resins are polymers whose constituent units are acid amides obtained by ring-opening polymerization of lactams, polycondensation of aminocarboxylic acids, or polycondensation of diamines and dibasic acids. Specific examples include polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, polyamide 6I, polyamide 6 / 66, polyamide 6T / 6I, polyamide 6 / 6T, polyamide 66 / 6T, polyamide 66 / 6T / 6I, polyamide MX, polytrimethylhexamethylene terephthalamide, polybis(4-aminocyclohexyl)methanedodecamide, polybis(3-methyl-4-aminocyclohexyl)methanedodecamide, and polyundecamethylenehexahydroterephthalamide. The "I" in the above text represents the isophthalic acid component, and the "T" represents the terephthalic acid component. Regarding polyamide resins, the description in paragraphs 0011 to 0013 of JP-A No. 2011-132550 can be referred to, the contents of which are incorporated herein by reference.

[0013] The polyamide resin used in this embodiment is preferably a xylylenediamine-based polyamide resin that is composed of diamine-derived structural units and dicarboxylic acid-derived structural units, and in which 70 mol % or more of the diamine-derived structural units are derived from xylylenediamine. The diamine-derived structural units of the xylylenediamine-based polyamide resin are more preferably 75 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably 99 mol% or more, of xylylenediamine (preferably paraxylylenediamine and / or metaxylylenediamine, more preferably paraxylylenediamine).

[0014] The xylylenediamine is preferably paraxylylenediamine and / or metaxylylenediamine. The xylylenediamine preferably contains 0 to 100 mol% metaxylylenediamine and 100 to 0 mol% paraxylylenediamine (however, the total of metaxylylenediamine and paraxylylenediamine does not exceed 100 mol%), more preferably 0 to 90 mol% metaxylylenediamine and 100 to 10 mol% paraxylylenediamine, even more preferably 0 to 50 mol% metaxylylenediamine and 100 to 50 mol% paraxylylenediamine, and even more preferably 0 to 20 mol% metaxylylenediamine and 100 to 80 mol% paraxylylenediamine. In the xylylenediamine-based polyamide resin, the total of the constitutional units derived from paraxylylenediamine and the constitutional units derived from metaxylylenediamine preferably accounts for 80 mol % or more, more preferably 85 mol % or more, even more preferably 90 mol % or more, still more preferably 95 mol % or more, still more preferably 98 mol % or more, and still more preferably 99 mol % or more of the constitutional units derived from diamine. The upper limit of the total of the constitutional units derived from paraxylylenediamine and the constitutional units derived from metaxylylenediamine is 100 mol %.

[0015] Diamines other than metaxylylenediamine and paraxylylenediamine that can be used as raw diamine components for xylylenediamine-based polyamide resins include aliphatic diamines such as tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine; 1,3-bis( Examples of the diamine include alicyclic diamines such as bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminomethyl)decalin, and bis(aminomethyl)tricyclodecane; and diamines having an aromatic ring such as bis(4-aminophenyl)ether, paraphenylenediamine, and bis(aminomethyl)naphthalene. These diamines can be used alone or in combination of two or more.

[0016] On the other hand, the dicarboxylic acid-derived structural units of the xylylenediamine-based polyamide resin are preferably 70 mol% or more, more preferably 75 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably 99 mol% or more, of which the structural units are derived from an α,ω-linear aliphatic dicarboxylic acid preferably having 4 to 20 carbon atoms (preferably sebacic acid).

[0017] Examples of α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms that are suitable for use as the raw dicarboxylic acid component of xylylenediamine-based polyamide resins include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, undecanedioic acid, and 1,12-dodecanedioic acid. These can be used alone or in combination of two or more. Among these, at least one of adipic acid, sebacic acid, and 1,12-dodecanedioic acid is preferred, as the melting point of the polyamide resin falls within a range suitable for molding and processing. Adipic acid and / or sebacic acid is more preferred, and sebacic acid is even more preferred.

[0018] Examples of dicarboxylic acid components other than those mentioned above include phthalic acid compounds such as isophthalic acid, terephthalic acid, and orthophthalic acid, and isomers of naphthalenedicarboxylic acid such as 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid, and these can be used alone or in combination of two or more.

[0019] In this embodiment, the polyamide resin preferably contains diamine-derived structural units and dicarboxylic acid-derived structural units, in which 70 mol % or more of the diamine-derived structural units are derived from paraxylylenediamine and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from an α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and more preferably contains a xylylenediamine-based polyamide resin in which 90 mol % or more of the diamine-derived structural units are derived from paraxylylenediamine and 90 mol % or more of the dicarboxylic acid-derived structural units are derived from sebacic acid. Such xylylenediamine-based polyamide resins are preferred because they have a high degree of crystallinity, a high melting point, and excellent dimensional stability.

[0020] Although the xylylenediamine-based polyamide resin is primarily composed of diamine-derived structural units and dicarboxylic acid-derived structural units, other structural units are not completely excluded, and it goes without saying that it may contain structural units derived from lactams such as ε-caprolactam and laurolactam, and aliphatic aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid. Here, "major component" refers to the structural units constituting the xylylenediamine-based polyamide resin in which the total number of diamine-derived structural units and dicarboxylic acid-derived structural units is the largest among all structural units. In this embodiment, the total of the diamine-derived structural units and dicarboxylic acid-derived structural units in the xylylenediamine-based polyamide resin preferably accounts for 90% by mass or more of all structural units, more preferably 95% by mass or more, even more preferably 97% by mass or more, and even more preferably 99% by mass or more.

[0021] It is also preferable to use a polyamide resin produced using biomass raw materials (biomass polyamide resin) as the xylylenediamine-based polyamide resin, which can reduce the environmental impact. Bio-adipic acid can be used as a biomass raw material for xylylenediamine-based polyamide resins. Mass-balance certified (ISCC PLUS) adipic acid can also be used. Mass-balance certification means that the amount of renewable or bio-based raw materials used at each factory or production facility, and the amount of products produced or shipped are quantified, along with the quality, and guaranteed.

[0022] The content of the xylylenediamine-based polyamide resin in 100 parts by mass of the polyamide resin in the resin composition of this embodiment is preferably 90 parts by mass or more, more preferably 95 parts by mass or more, and even more preferably 97 parts by mass or more, and may be 100 parts by mass or less.

[0023] The melting point of the polyamide resin is preferably 150°C or higher, more preferably 250°C or higher, and even more preferably 280°C or higher, and is preferably 350°C or lower, more preferably 330°C or lower, and even more preferably 300°C or lower.

[0024] The lower limit of the number average molecular weight (Mn) of the polyamide resin is preferably 6,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more, and is preferably 100,000 or less, more preferably 50,000 or less. Within such ranges, the heat resistance, elastic modulus, dimensional stability, and moldability are improved.

[0025] <<Polycarbonate resin>> The polycarbonate resin is not particularly limited, and any of aromatic polycarbonate, aliphatic polycarbonate, and aromatic-aliphatic polycarbonate can be used. Among them, aromatic polycarbonate is preferred, and further, thermoplastic aromatic polycarbonate polymers or copolymers obtained by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid are more preferred.

[0026] Examples of aromatic dihydroxy compounds include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), tetramethylbisphenol A, bis(4-hydroxyphenyl)-p-diisopropylbenzene, hydroquinone, resorcinol, and 4,4-dihydroxydiphenyl, with bisphenol A being preferred. Furthermore, for the purpose of preparing a highly flame-retardant composition, compounds in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compounds, or polymers or oligomers having a siloxane structure and containing phenolic OH groups at both ends, can be used.

[0027] Preferred examples of the polycarbonate resin used in this embodiment include polycarbonate resins derived from 2,2-bis(4-hydroxyphenyl)propane; and polycarbonate copolymers derived from 2,2-bis(4-hydroxyphenyl)propane and other aromatic dihydroxy compounds.

[0028] The method for producing the polycarbonate resin is not particularly limited, and in this embodiment, polycarbonate resins produced by any method, such as a phosgene method (interfacial polymerization method) or a melting method (ester interchange method), can be used. In addition, in this embodiment, polycarbonate resins produced by a general melting method production process followed by a process of adjusting the amount of OH groups in the terminal groups may also be used.

[0029] Furthermore, the polycarbonate resin used in this embodiment may be not only a polycarbonate resin as a virgin raw material, but also a polycarbonate resin regenerated from used products, that is, a so-called material-recycled polycarbonate resin.

[0030] For further details regarding the polycarbonate resin used in this embodiment, see, for example, the descriptions in paragraphs 0018 to 0066 of JP-A No. 2012-072338 and paragraphs 0011 to 0018 of JP-A No. 2015-166460, the contents of which are incorporated herein by reference.

[0031] <<Polyester resin>> Examples of polyester resins include polyethylene terephthalate resins and polybutylene terephthalate resins. As is well known, polyethylene terephthalate resins and polybutylene terephthalate resins are produced on a large scale by reacting terephthalic acid or ester with ethylene glycol or 1,4-butanediol, and are distributed on the market. In this embodiment, these commercially available resins can be used. Some commercially available resins contain copolymer components other than the terephthalic acid component and the ethylene glycol component or 1,4-butanediol component. In this embodiment, resins containing a small amount of copolymer component, typically 10% by mass or less, preferably 5% by mass or less, can also be used. The intrinsic viscosity of polyethylene terephthalate resin is usually 0.4 to 1.0 dL / g, and preferably 0.5 to 1.0 dL / g. When the intrinsic viscosity is equal to or greater than the lower limit, the mechanical properties of the resin composition are less likely to deteriorate, and when it is equal to or less than the upper limit, fluidity is easily maintained. Note that all intrinsic viscosities are measured at 30°C in a phenol / tetrachloroethane (1 / 1 mass ratio) mixed solvent. The intrinsic viscosity of the polybutylene terephthalate resin is usually 0.5 to 1.5 dL / g, and preferably 0.6 to 1.3 dL / g. If the intrinsic viscosity is equal to or greater than the lower limit, it is easy to obtain a resin composition with excellent mechanical strength. If the intrinsic viscosity is equal to or less than the upper limit, the resin composition does not lose its fluidity, and tends to have excellent moldability. In addition, the amount of terminal carboxyl groups is preferably 30 meq / g or less.

[0032] The polybutylene terephthalate resin may be a polybutylene terephthalate resin modified by copolymerization. Specific preferred copolymers include polyester ether resins copolymerized with polyalkylene glycols, particularly polytetramethylene glycol, dimer acid copolymerized polybutylene terephthalate resins, and isophthalic acid copolymerized polybutylene terephthalate resins. These copolymers refer to those in which the copolymerization amount is 1 mol% or more but less than 50 mol% of the total polybutylene terephthalate resin segments. The copolymerization amount is preferably 2 to 50 mol%, more preferably 3 to 40 mol%, and particularly preferably 5 to 20 mol%. Reference is also made to paragraphs 0014 to 0022 of JP 2019-006866 A, which are incorporated herein by reference. In addition to the above, the polyester resin may be found in paragraphs 0013 to 0016 of JP-A-2010-174223, the contents of which are incorporated herein by reference. The resin composition used in the present embodiment may contain only one type of thermoplastic polyester resin, or may contain two or more types.

[0033] <<Styrene-based resin>> The styrene-based resin refers to at least one polymer selected from the group consisting of a styrene-based polymer made of a styrene-based monomer, a copolymer of a styrene-based monomer and another copolymerizable vinyl-based monomer, and a copolymer obtained by polymerizing a styrene-based monomer or a styrene-based monomer and another copolymerizable vinyl-based monomer in the presence of a rubber-based polymer, and among these, a copolymer with a rubber-based polymer is preferred.

[0034] Examples of rubbery polymers copolymerizable with styrene-based monomers include polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, acrylonitrile-butadiene random copolymers and block copolymers, acrylonitrile-butadiene copolymers, copolymers of acrylic acid alkyl esters or methacrylic acid alkyl esters with butadiene, copolymers of ethylene and α-olefins such as polybutadiene-polyisoprene diene copolymers, ethylene-isoprene random copolymers and block copolymers, and ethylene-butene random copolymers and block copolymers, copolymers of ethylene and α,β-unsaturated carboxylic acid esters such as ethylene-methacrylate copolymers and ethylene-butyl acrylate copolymers, ethylene-propylene-non-conjugated diene terpolymers such as ethylene-vinyl acetate copolymers and ethylene-propylene-hexadiene copolymers, acrylic rubbers, and composite rubbers consisting of polyorganosiloxane rubber and polyalkyl acrylate or methacrylate rubber. For details of styrene-based resins, please refer to the descriptions in paragraphs 0019 to 0029 of JP 2015-166460 A, which are incorporated herein by reference. The resin composition used in the present embodiment may contain only one type of styrene-based resin, or may contain two or more types.

[0035] <<Other resins, etc.>> For further details about the thermoplastic resin, please refer to paragraphs 0011 to 0028 of JP 2014-074162 A, the contents of which are incorporated herein by reference.

[0036] A first embodiment of the thermoplastic resin of this embodiment is an embodiment in which 90% by mass or more (more preferably 95% by mass or more, and even more preferably 99% by mass or more) of the (A) thermoplastic resin is a polyamide resin (preferably a xylylenediamine-based polyamide resin). A second embodiment of the thermoplastic resin of this embodiment is an embodiment in which 90 mass % or more of the thermoplastic resin (A) is a polycarbonate resin. A third embodiment of the thermoplastic resin of this embodiment is an embodiment in which the thermoplastic resin (A) is 85 to 65 mass % polycarbonate resin and 15 to 35 mass % styrene resin (particularly rubber-based resin such as ABS resin). The total of the polycarbonate resin and the styrene resin is preferably 90 mass % or more of the thermoplastic resin. A fourth embodiment of the thermoplastic resin of this embodiment is an embodiment in which 85 to 65 mass % of the thermoplastic resin (A) is a polycarbonate resin and 15 to 35 mass % is a polyester resin (particularly polyethylene terephthalate). The total of the polycarbonate resin and the polyester resin is preferably 90 mass % or more of the thermoplastic resin. A fifth embodiment of the thermoplastic resin of this embodiment is an embodiment in which the thermoplastic resin (A) contains 15 to 45 mass% polybutylene terephthalate, 15 to 45 mass% isophthalic acid-modified polybutylene terephthalate, and 70 to 10 mass% polyamide resin (particularly aliphatic polyamide resin). The total of the polybutylene terephthalate, isophthalic acid-modified polybutylene terephthalate, and polyamide resin is preferably 90 mass% or more.

[0037] The resin composition of the present embodiment contains 10% by mass or more of (A) thermoplastic resin, preferably 30% by mass or more, more preferably 35% by mass or more, even more preferably 38% by mass or more, and even more preferably 40% by mass or more, and contains 90% by mass or less, preferably 70% by mass or less, even more preferably 55% by mass or less, even more preferably 50% by mass or less, and even more preferably 48% by mass or less. The resin composition of the present embodiment may contain only one type of (A) thermoplastic resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0038] <(B) Laser Direct Structuring Additive> The resin composition of the present embodiment contains (B) a laser direct structuring additive (LDS additive). By configuring in this way, a resin composition with excellent plating properties can be obtained. The LDS additive in this embodiment refers to a compound that can selectively form a plating only in the laser-irradiated area when 10 parts by mass of an additive considered to be an LDS additive is added to 100 parts by mass of polyamide resin, irradiated with a 1064 nm YAG laser at an output of 10 W, a frequency of 80 kHz, and a speed of 3 m / s, and then immersed in an electroless plating bath as a plating process. The LDS additive used in this embodiment may be a synthetic product or a commercially available product. In addition to commercially available LDS additives, commercially available products may also be substances sold for other purposes as long as they meet the requirements of the LDS additive in this embodiment. A single LDS additive may be used, or two or more may be used in combination.

[0039] A first embodiment of the LDS additive used in this embodiment is a compound containing copper and chromium. The LDS additive of the first embodiment preferably contains 10 to 30 mass% of copper. Also, it preferably contains 15 to 50 mass% of chromium. The LDS additive of the first embodiment is preferably an oxide containing copper and chromium, and more preferably copper-chromium oxide.

[0040] The preferred copper and chromium content is in the spinel structure, which is one of the typical crystal structures found in AB2O4 type compounds (A and B are metal elements) in double oxides.

[0041] The LDS additive of the first embodiment may contain trace amounts of other metals in addition to copper and chromium. Examples of other metals include antimony, tin, lead, indium, iron, cobalt, nickel, zinc, cadmium, silver, bismuth, arsenic, manganese, magnesium, and calcium, with manganese being preferred. These metals may be present as oxides. A preferred example of the LDS additive of the first embodiment is an LDS additive in which the content of metal oxides other than copper chromium oxide is 10 mass % or less.

[0042] A second embodiment of the LDS additive used in this embodiment is an oxide containing tin and at least one of antimony and phosphorus, preferably an oxide containing antimony and tin.

[0043] The LDS additive of the second embodiment preferably has a tin content greater than the phosphorus and antimony contents, and more preferably the amount of tin relative to the total amount of tin, phosphorus, and antimony is 80 mass % or more.

[0044] In particular, as the LDS additive of the second embodiment, an oxide containing antimony and tin is preferable, an oxide in which the tin content is higher than the antimony content is more preferable, and an oxide in which the amount of tin relative to the total amount of tin and antimony is 80 mass% or more is even more preferable.

[0045] More specifically, examples of the LDS additive of the second embodiment include antimony-doped tin oxide, antimony oxide-doped tin oxide, phosphorus-doped tin oxide, and phosphorus oxide-doped tin oxide. Antimony-doped tin oxide and antimony oxide-doped tin oxide are preferred, and antimony oxide-doped tin oxide is more preferred. For example, in an LDS additive containing phosphorus and tin oxide, the phosphorus content is 1 to 20 mass%. In an LDS additive containing antimony and tin oxide, the antimony content is preferably 1 to 20 mass%. In an LDS additive containing phosphorus, antimony, and tin oxide, the phosphorus content is preferably 0.5 to 10 mass% and the antimony content is preferably 0.5 to 10 mass%.

[0046] A third embodiment of the LDS additive used in this embodiment contains at least two metals and has a resistivity of 5×10 3 It is preferable that the conductive oxide has a resistivity of 8×10 Ω·cm or less.2 Ω·cm or less is preferable, and 7×10 2 Ω·cm or less is more preferable, and 5×10 2 It is more preferable that the resistivity is Ω·cm or less. There is no particular lower limit, but for example, 1×10 1 It may be Ω·cm or more, and even 1×10 2 It may be Ω·cm or more. The resistivity of the conductive oxide in this embodiment generally refers to powder resistivity, and is measured by placing 10 g of fine powder of the conductive oxide in a cylinder with an inner diameter of 25 mm and coated with Teflon (registered trademark) on the inside, and measuring 100 kgf / cm 2 The pressure can be increased to 20% (filling rate 20%) and measured using a Yokogawa Electric "3223" tester.

[0047] The LDS additive used in the third embodiment has a resistivity of 5×10 3 There are no particular limitations as long as the oxide contains a conductive oxide with a resistivity of Ω·cm or less, but it is preferable that the oxide contains at least two metals, specifically, a metal from group n (n is an integer from 3 to 16) and a metal from group n+1 of the periodic table. n is more preferably an integer from 10 to 13, and even more preferably 12 or 13. In the LDS additive used in the third embodiment, when the total content of the metals in Group n (n is an integer from 3 to 16) and Group n+1 of the periodic table in the LDS additive is taken as 100 mol %, the content of one of the metals is preferably 15 mol % or less, more preferably 12 mol % or less, and even more preferably 10 mol % or less. There is no particular lower limit, but a content of 0.0001 mol % or more is preferred. By setting the content of two or more metals within these ranges, plating properties can be improved. In this embodiment, an n-group metal oxide doped with a Group n+1 metal is particularly preferred. Furthermore, the LDS additive used in the third embodiment preferably has 98 mass % or more of the metal components contained in the LDS additive composed of the metals of Group n and Group n+1 of the periodic table.

[0048] Examples of metals in the n-group of the periodic table include Group 3 (scandium, yttrium), Group 4 (titanium, zirconium, etc.), Group 5 (vanadium, niobium, etc.), Group 6 (chromium, molybdenum, etc.), Group 7 (manganese, etc.), Group 8 (iron, ruthenium, etc.), Group 9 (cobalt, rhodium, iridium, etc.), Group 10 (nickel, palladium, platinum), Group 11 (copper, silver, gold, etc.), Group 12 (zinc, cadmium, etc.), Group 13 (aluminum, gallium, indium, etc.), Group 14 (germanium, tin, etc.), Group 15 (arsenic, antimony, etc.), and Group 16 (selenium, tellurium, etc.). Among these, metals in Group 12 (n=12) are preferred, and zinc is more preferred.

[0049] Examples of metals in Group n+1 of the periodic table include Group 4 (titanium, zirconium, etc.), Group 5 (vanadium, niobium, etc.), Group 6 (chromium, molybdenum, etc.), Group 7 (manganese, etc.), Group 8 (iron, ruthenium, etc.), Group 9 (cobalt, rhodium, iridium, etc.), Group 10 (nickel, palladium, platinum), Group 11 (copper, silver, gold, etc.), Group 12 (zinc, cadmium, etc.), Group 13 (aluminum, gallium, indium, etc.), Group 14 (germanium, tin, etc.), Group 15 (arsenic, antimony, etc.), and Group 16 (selenium, tellurium, etc.). Among these, metals in Group 13 (n+1=13) are preferred, aluminum or gallium is more preferred, and aluminum is even more preferred.

[0050] The LDS additive used in the third embodiment may contain a metal other than a conductive metal oxide. Examples of metals other than a conductive oxide include antimony, titanium, indium, iron, cobalt, nickel, cadmium, silver, bismuth, arsenic, manganese, chromium, magnesium, and calcium. These metals may exist as oxides. The content of each of these metals is preferably 0.01% by mass or less of the LDS additive.

[0051] Among the above, in this embodiment, the LDS additive preferably contains at least one of copper, antimony, tin, aluminum, and zinc, and more preferably contains copper. Therefore, the LDS additive of the first embodiment is more preferable.

[0052] The number average particle size of the LDS additive used in this embodiment is preferably 0.01 to 100 μm, more preferably 0.05 to 30 μm, and even more preferably 0.05 to 15 μm. By adjusting the number average particle size to such a range, the plating surface can be made more uniform.

[0053] The resin composition of the present embodiment contains (B) an LDS additive (preferably copper chromium oxide) in an amount of 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 7% by mass or more, and also contains 20% by mass or less, preferably 17% by mass or less, and even more preferably 12% by mass or less. The resin composition of this embodiment may contain only one type of (B) LDS additive, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0054] <(C) Phosphorus-based flame retardants> The resin composition of this embodiment contains (C) a phosphorus-based flame retardant. By blending a phosphorus-based flame retardant, it is possible to improve not only flame retardancy but also plating properties. Furthermore, unlike halogen-based flame retardants, the resin composition can be configured without a flame retardant assistant. Examples of phosphorus-based flame retardants include phosphinates, diphosphinates, melamine polyphosphate, condensed phosphate esters, and phosphazene compounds. Among these, at least one of phosphinates and diphosphinates is preferred, and it is more preferred to include a phosphinate. By using a phosphinate and / or a diphosphinate, the deflection temperature under load can be maintained at a higher level.

[0055] In this embodiment, it is preferable that the (C) phosphorus-based flame retardant further contains at least one of a compound represented by the following formula (I) and a compound represented by the following formula (II). [ka] (In formula (I), R 1 and R 2 each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. M represents a calcium ion, an aluminum ion, a magnesium ion, or a zinc ion. m is a natural number representing the valence of M. [ka] (In formula (II), R 4 and R 5 R each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. 3 represents a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 10 carbon atoms, or an arylalkylene group having 7 to 10 carbon atoms. M represents a calcium ion, an aluminum ion, a magnesium ion, or a zinc ion. n is a natural number representing the valence of M. n, a, and b are natural numbers that satisfy the relational expression 2×b=n×a.

[0056] In formula (I), R 1 and R 2 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and are preferably a methyl group, an ethyl group, a propyl group, or a phenyl group. M represents a calcium ion, an aluminum ion, a magnesium ion, or a zinc ion. m is a natural number representing the valence of M, and is preferably 2 or 3.

[0057] In formula (II), R 4 and R 5R each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, a propyl group, or a phenyl group. 3 represents a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 10 carbon atoms, or an arylalkylene group having 7 to 10 carbon atoms, and is preferably a methylene group, an ethylene group, a propylene group, or a phenylene group. M represents a calcium ion, an aluminum ion, a magnesium ion, or a zinc ion. n is a natural number representing the valence of M. n, a, and b are natural numbers that satisfy the relational expression 2×b=n×a. n is preferably 2 or 3. b is preferably 1, 2, or 3, and more preferably 1 or 3. a is preferably 1 or 2.

[0058] Specific examples of phosphinates or diphosphinates include those produced in an aqueous medium using phosphinic acid and a metal carbonate, metal hydroxide, or metal oxide. Phosphinates or diphosphinates are basically monomeric compounds, but depending on the reaction conditions and environment, they may become polymeric phosphinates with a condensation degree of 1 to 3.

[0059] Examples of phosphinic acids or diphosphinic acids include dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methanedi(methylphosphinic acid), benzene-1,4-di(methylphosphinic acid), methylphenylphosphinic acid, and diphenylphosphinic acid.

[0060] Examples of the phosphinate include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, zinc methyl-n-propylphosphinate, calcium methylphenylphosphinate, magnesium methylphenylphosphinate, aluminum methylphenylphosphinate, zinc methylphenylphosphinate, calcium diphenylphosphinate, magnesium diphenylphosphinate, aluminum diphenylphosphinate, and zinc diphenylphosphinate.

[0061] Examples of diphosphinates include calcium methane di(methylphosphinate), magnesium methane di(methylphosphinate), aluminum methane di(methylphosphinate), zinc methane di(methylphosphinate), calcium benzene-1,4-di(methylphosphinate), magnesium benzene-1,4-di(methylphosphinate), aluminum benzene-1,4-di(methylphosphinate), and zinc benzene-1,4-di(methylphosphinate).

[0062] Among these phosphinates and diphosphinates, aluminum ethylmethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate are particularly preferred from the viewpoints of flame retardancy and electrical properties. Specific commercial products include EXOLIT OP 1230 (aluminum phosphinate) and EXOLIT OP 1400 (both trade names) manufactured by Clariant.

[0063] The content of the (C) phosphorus-based flame retardant (preferably at least one of phosphinate and diphosphinate) in the resin composition of this embodiment is 1.0% by mass or more, preferably 2.0% by mass or more, more preferably 2.5% by mass or more, even more preferably 3.0% by mass or more, and even more preferably 4.0% by mass or more, and is 7.9% by mass or less, preferably 7.0% by mass or less, more preferably 6.5% by mass or less, and even more preferably 6.0% by mass or less. By setting the amount of the (C) phosphorus-based flame retardant to the above-mentioned lower limit or more, the flame retardant effect is fully exerted and plating ability tends to be improved. On the other hand, by setting the amount of the (C) phosphorus-based flame retardant to the above-mentioned upper limit or less, the deflection temperature under load tends to be further improved. The resin composition of the present embodiment may contain only one type of (C) phosphorus-based flame retardant, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0064] The resin composition of this embodiment is preferably substantially free of halogen-based flame retardants. "Substantially free" means that the content of halogen-based flame retardants is less than 10% by mass of the content of (C) phosphorus-based flame retardant, preferably less than 7% by mass, more preferably less than 5% by mass, even more preferably less than 3% by mass, even more preferably less than 1% by mass, and even more preferably less than 0.1% by mass. The resin composition of this embodiment preferably is substantially free of flame retardants other than the (C) phosphorus-based flame retardant. "Substantially free" means that the content of flame retardants other than the (C) phosphorus-based flame retardant is less than 10% by mass of the (C) phosphorus-based flame retardant, preferably less than 7% by mass, more preferably less than 5% by mass, even more preferably less than 3% by mass, even more preferably less than 1% by mass, and even more preferably less than 0.1% by mass.

[0065] <(D) Graphite> The resin composition of the present embodiment contains graphite. The graphite in this embodiment is intended to include graphite, graphene, and graphite. Graphite is a material made of carbon and has a hexagonal crystal structure. Graphite may be natural graphite or artificial graphite. Graphite is commercially available from Nippon Graphite Co., Ltd., Ito Graphite Industries Co., Ltd., and the like. In contrast, carbon black is a material made of carbon, but it has an amorphous and non-crystalline structure and is not classified as graphite. The graphite is preferably in a flake form. The flake form also includes what is called a scale form. By using flake-form graphite, the effects of this embodiment are more effectively exhibited. The number average particle diameter of graphite is preferably 1 to 100 μm, more preferably 3 to 50 μm, and even more preferably 5 to 30 μm. When the graphite is in a non-particulate form, such as a flake form, the number average particle diameter is the length of the longest part. The number average particle diameter of graphite is calculated from the measured values ​​obtained by randomly selecting graphite particles to be measured for particle diameter from an image obtained by observation with an electron microscope and measuring the particle diameter. The observation is performed at a magnification of 1,000x, with 1,000 or more particles measured. The number average particle diameter of graphite is the circle equivalent diameter measured by the above microscope observation, and the number average value is used.

[0066] The resin composition of this embodiment contains (D) graphite in the resin composition at 0.3% by mass or more, preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and even more preferably 1.0% by mass or more, and contains 7.0% by mass or less, preferably 6.0% by mass or less, and may be 5.0% by mass or less, or may be 3.0% by mass or less. By setting the content at or above the lower limit, the dielectric constant can be increased. Meanwhile, by setting the content at or below the upper limit, an increase in the dielectric loss tangent can be effectively suppressed and plating properties can be improved. The resin composition of the present embodiment may contain only one type of (D) graphite, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition of this embodiment may be configured to be substantially free of carbon filler, which means that the carbon filler is less than 10% by mass of the (D) graphite content, preferably less than 5% by mass, more preferably less than 3% by mass, even more preferably less than 1% by mass, and even more preferably less than 0.1% by mass.

[0067] <Blend ratio> The resin composition of the present embodiment contains (A) a thermoplastic resin, (B) a laser direct structuring additive, (C) a phosphorus-based flame retardant, and (D) graphite, but the total of these does not exceed 100 mass%. When the resin composition of this embodiment contains (E) inorganic reinforcing fibers, the total amount of (A) thermoplastic resin, (B) laser direct structuring additive, (C) phosphorus-based flame retardant, (D) graphite, and (E) inorganic reinforcing fibers does not exceed 100 mass%.

[0068] The resin composition of this embodiment is prepared so that the total of (A) thermoplastic resin, (B) laser direct structuring additive, (C) phosphorus-based flame retardant, and (D) graphite, as well as components blended as necessary, is 100% by mass. In the resin composition of this embodiment, the total of (A) thermoplastic resin, (B) laser direct structuring additive, (C) phosphorus-based flame retardant, (D) graphite, and (E) inorganic reinforcing fiber preferably accounts for 90% by mass or more of the resin composition, more preferably 94% by mass or more, even more preferably 96% by mass or more, and even more preferably 98% by mass or more. In the resin composition of the present embodiment, the total of (A) thermoplastic resin, (B) laser direct structuring additive, (C) phosphorus-based flame retardant, (D) graphite, (E) inorganic reinforcing fiber, anti-drip agent, release agent, and nucleating agent preferably accounts for 90% by mass or more of the resin composition, more preferably 95% by mass or more, even more preferably 97% by mass or more, and even more preferably 99% by mass or more.

[0069] As described above, it is preferable to precisely adjust the blending ratio of the (B) LDS additive, the (C) phosphorus-based flame retardant, and the (D) graphite in the resin composition of this embodiment. By precisely adjusting the mass ratio of these components, the effects of the present invention tend to be more effectively exhibited. Specifically, the mass ratio of the total amount of the laser direct structuring additive (B) and the phosphorus-based flame retardant (C) to the graphite (D) contained in the resin composition, {(C) + (D)} / (B), is preferably less than 1.00, more preferably less than 0.90, even more preferably less than 0.80, and even more preferably less than 0.75. It is also preferably 0.30 or greater, more preferably 0.40 or greater, even more preferably greater than 0.50, even more preferably 0.55 or greater, even more preferably greater than 0.60, and even more preferably greater than 0.65. By setting the mass ratio at or above the lower limit, high dielectric constant tends to be achieved while maintaining flame retardancy. Furthermore, by setting the mass ratio at or below the upper limit, plating ability and high deflection temperature under load tend to be more effectively improved.

[0070] <(E) Inorganic reinforced fiber> The resin composition of the present embodiment preferably contains (E) inorganic reinforcing fibers. (E) Examples of inorganic reinforcing fibers include carbon fibers and glass fibers, and glass fibers are preferred.

[0071] In this embodiment, the inorganic reinforcing fiber refers to a fibrous inorganic material, and more specifically, it is preferably a chopped shape obtained by bundling 1,000 to 10,000 inorganic reinforcing fibers and cutting them to a predetermined length. In this embodiment, the inorganic reinforcing fibers preferably have a number average fiber length (cut length) of 0.5 to 10 mm, more preferably 1 to 5 mm. By using inorganic reinforcing fibers with such a number average fiber length, mechanical strength can be further improved. The number average fiber length is calculated from the measured values ​​obtained by randomly selecting inorganic reinforcing fibers to be measured for fiber length from an image obtained by observation with an optical microscope and measuring the long sides of the fibers. The observation is performed at a magnification of 20 times, and the number of fibers measured is 1,000 or more. This roughly corresponds to the cut length. The cross section of the inorganic reinforcing fiber may be any shape, such as a circle, an ellipse, an oval, a rectangle, a rectangle with semicircles on both short sides, or a cocoon shape. The number-average fiber diameter of the inorganic reinforcing fiber is preferably 4.0 μm or more, more preferably 4.5 μm or more, and even more preferably 5.0 μm or more. The upper limit of the number-average fiber diameter of the inorganic reinforcing fiber is preferably 15.0 μm or less, more preferably 12.0 μm or less. By using inorganic reinforcing fibers having a number-average fiber diameter within this range, molded articles with excellent plating properties can be obtained even after wet heat treatment. Furthermore, high plating properties can be maintained even when the molded article is stored for a long period of time or heat-treated for a long period of time. The number-average fiber diameter of the inorganic reinforcing fiber is calculated from the measured values ​​obtained by randomly selecting inorganic reinforcing fibers to be measured for fiber diameter from an image obtained by observation with an electron microscope, measuring the fiber diameter near the center. The observation is performed at a magnification of 1,000x, and the number of fibers measured is 1,000 or more. The number-average fiber diameter of inorganic reinforcing fibers having a cross section other than a circle is the number-average fiber diameter when converted into a circle with the same area as the cross section.

[0072] Next, the glass fiber preferably used in this embodiment will be described. The glass fibers used are typically obtained by melt spinning commonly available glass fibers such as E-glass, C-glass, A-glass, S-glass, and alkali-resistant glass. However, any material that can be used to form glass fibers is not particularly limited. In this embodiment, E-glass is preferably used. The glass fibers used in this embodiment are preferably surface-treated with a surface treatment agent such as a silane coupling agent, for example, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, or γ-aminopropyltriethoxysilane. The amount of the surface treatment agent applied is preferably 0.01 to 1% by mass of the glass fiber. Furthermore, if necessary, glass fibers may be surface-treated with a lubricant such as a fatty acid amide compound or silicone oil, an antistatic agent such as a quaternary ammonium salt, a film-forming resin such as an epoxy resin or urethane resin, or a mixture of a film-forming resin with a heat stabilizer or flame retardant. The glass fibers used in this embodiment may be bundled with a sizing agent. In this case, epoxy-based or urethane-based sizing agents are preferred.

[0073] Glass fibers are commercially available, such as T-187, T-286H, T-756H, and T-289H manufactured by Nippon Electric Glass Co., Ltd., DEFT2A manufactured by Owens Corning, HP3540 manufactured by PPG, and CSG3PA820 manufactured by Nitto Boseki Co., Ltd.

[0074] When the resin composition of the present embodiment contains (E) inorganic reinforcing fibers, it preferably contains 10% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, even more preferably 30% by mass or more, and even more preferably 35% by mass or more, and it preferably contains 60% by mass or less, more preferably 50% by mass or less, and may even be 45% by mass or less. The resin composition of the present embodiment may contain only one type of (E) inorganic reinforcing fiber, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0075] <Other ingredients> The resin composition of this embodiment may contain other components in addition to those described above. Examples of other components include nucleating agents, anti-drip agents, release agents, light stabilizers, heat stabilizers, alkalis, elastomers, titanium oxide, antioxidants, hydrolysis resistance improvers, delustering agents, UV absorbers, plasticizers, dispersants, antistatic agents, coloring inhibitors, antigelling agents, and colorants. For details, see paragraphs

[0130] to

[0155] of Japanese Patent No. 4894982 and paragraphs

[0047] to

[0103] of International Publication No. 2021 / 241471, the contents of which are incorporated herein by reference. The total amount of these components is preferably less than 20% by mass of the resin composition, more preferably less than 10% by mass, even more preferably less than 5% by mass, and even more preferably less than 3% by mass. Each of these components may be used alone, or two or more may be used in combination.

[0076] <<Nucleating agent>> The resin composition of the present embodiment may further contain a nucleating agent. The type of nucleating agent is not particularly limited, but talc, boron nitride, mica, kaolin, calcium carbonate, barium sulfate, silicon nitride, potassium titanate, and molybdenum disulfide are preferred, with talc and boron nitride being more preferred, and talc being even more preferred. Adding talc can increase the plating growth rate. Furthermore, adding talc can improve the plating properties of molded products even when the LDS additive content is reduced. Talc may be surface-treated with at least one compound selected from polyorganohydrogensiloxanes and organopolysiloxanes. In this case, the amount of the siloxane compound attached to the talc is preferably 0.1 to 5% by mass of the talc. The number average particle size of the nucleating agent is preferably 1 to 50 μm, more preferably 2 to 25 μm, and even more preferably 2 to 10 μm. When the nucleating agent is not particulate, such as in a scale-like form, the number average particle size is the length of the longest part. The number average particle size of talc is calculated from the measured values ​​obtained by randomly selecting talc particles to be measured for particle size from an image obtained by observation with an electron microscope and measuring the particle size. The observation magnification is 1,000x, and the number of measurements is 1,000 or more.

[0077] When the resin composition of the present embodiment contains a nucleating agent, the content thereof in the resin composition is preferably 0.01 to 5 mass %, more preferably 0.1 to 1 mass %, and even more preferably 0.1 to 0.5 mass %. The resin composition of the present embodiment may contain only one type of nucleating agent, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0078] <<Anti-drip agent>> The resin composition of the present embodiment may contain an anti-drip agent. By containing an anti-drip agent, it is possible to further improve flame retardancy and maintain high plating performance. As the anti-drip agent, a fluoropolymer is preferred, and examples of the fluoropolymer include fluoroolefin resins. Fluoroolefin resins are generally polymers (including copolymers) containing a fluoroethylene structure. Specific examples include difluoroethylene resins, tetrafluoroethylene resins, tetrafluoroethylene / hexafluoropropylene resins, and tetrafluoroethylene / perfluoroalkyl vinyl ether resins. Of these, tetrafluoroethylene resins are preferred. As the fluoroethylene resin, a fluoroethylene resin having fibril-forming ability is preferred.

[0079] Examples of fluoroethylene resins capable of forming fibrils include "Teflon (registered trademark) 6J," "Teflon (registered trademark) 640J," and "Teflon (registered trademark) 6C" manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd., and "Polyflon MPAF201L," "Polyflon MPAF103," and "Polyflon MPAFA500H" manufactured by Daikin Industries, Ltd. Furthermore, examples of commercially available aqueous dispersions of fluoroethylene resins include "Teflon (registered trademark) 30J" and "Teflon (registered trademark) 31-JR" manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd., and "Fluon D-1" manufactured by Daikin Industries, Ltd.

[0080] Furthermore, fluoroethylene polymers having a multilayer structure obtained by polymerizing vinyl monomers can also be used. Examples of such fluoroethylene polymers include polystyrene-fluoroethylene polymer, polystyrene-acrylonitrile-fluoroethylene polymer, polymethyl methacrylate-fluoroethylene polymer, and polybutyl methacrylate-fluoroethylene polymer. Specific examples include "Metablen A-3800" manufactured by Mitsubishi Chemical Corporation and "Brendex 449" manufactured by GE Specialty Chemicals.

[0081] When the resin composition of this embodiment contains an anti-drip agent, the content thereof is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, even more preferably 0.03 parts by mass or more, and preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, even more preferably 1.0 part by mass or less, and even more preferably 0.7 parts by mass or less, relative to 100 parts by mass of the thermoplastic resin (A). By making the content equal to or greater than the lower limit, the effect of improving flame retardancy is more effectively exerted, and plating ability tends to be further improved. The resin composition of the present embodiment may contain only one type of anti-drip agent, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0082] <<Release Agent>> The resin composition of this embodiment may further contain a release agent. The release agent is primarily used to improve productivity during molding of the resin composition. Examples of the release agent include aliphatic carboxylic acid amides, aliphatic carboxylic acids, aliphatic carboxylic acid metal salts, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number-average molecular weight of 200 to 15,000, polysiloxane-based silicone oils, ethylene bisstearic acid amide, and distearyl ketone.

[0083] For details about the release agent, please refer to the descriptions in paragraphs 0037 to 0042 of JP 2016-196563 A and paragraphs 0048 to 0058 of JP 2016-078318 A, the contents of which are incorporated herein by reference.

[0084] When a release agent is added, the lower limit of the content of the release agent relative to the resin composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and the upper limit is preferably 2.0% by mass or less, more preferably 1.5% by mass or less. By setting the content within such ranges, it is possible to improve the mold releasability and prevent mold contamination during injection molding. The release agent may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total amount is within the above range.

[0085] <Physical properties of resin composition> The resin composition of this embodiment preferably has a high deflection temperature under load. Specifically, when the resin composition of this embodiment is molded into an ISO tensile test piece (thickness 4 mm), the deflection temperature under load under a bending stress of 1.80 MPa in accordance with ISO 75-1 and 2 is preferably 255°C or higher, more preferably 256°C or higher, and even more preferably 257°C or higher. There is no particular upper limit for the deflection temperature under load, but a temperature of 280°C or lower is practical, and even a temperature of 270°C or lower will sufficiently satisfy the required performance. The resin composition of this embodiment preferably has a low dielectric constant (Dk). Specifically, the dielectric constant at 2.45 GHz of a plate test piece (100 mm on a side, 2 mm thick) formed from the resin composition of this embodiment is preferably 10.0 or less, more preferably 6.7 or less, and more preferably 6.5 or less. There is no particular lower limit to the dielectric constant, but a value of 1.0 or more is practical. The resin composition of this embodiment preferably has excellent flame retardancy. Specifically, the resin composition of this embodiment is molded into a 0.8 mm thick test piece, and the flame retardancy measured in accordance with the UL-94 test preferably satisfies V-0. The deflection temperature under load, Dk and flame retardancy are measured according to the description in the examples below.

[0086] <Method of manufacturing resin composition> As a method for producing the resin composition of the present embodiment, any method can be adopted. For example, a method is exemplified in which (A) thermoplastic resin, (B) laser direct structuring additive, (C) phosphorus-based flame retardant, and (D) graphite are mixed using a mixing means such as a V-type blender to prepare a lump blend, which is then melt-kneaded in a vented extruder and pelletized. Alternatively, a two-stage kneading method is exemplified in which components other than (E) inorganic reinforcing fiber are first thoroughly mixed, which is then melt-kneaded in a vented extruder to produce pellets, which are then mixed with (E) inorganic reinforcing fiber, and the pellets are then melt-kneaded in a vented extruder. Furthermore, a method can be mentioned in which components other than (E) inorganic reinforcing fiber are thoroughly mixed in advance using a V-type blender or the like, and the mixture is fed from the first chute of a vented twin-screw extruder, and (E) inorganic reinforcing fiber is fed from the second chute midway through the extruder, followed by melt-kneading and pelletization.

[0087] The screw configuration of the kneading zone of the extruder is preferably such that an element that promotes kneading is disposed on the upstream side and an element that has the ability to increase pressure is disposed on the downstream side. Examples of elements that promote kneading include a progressive kneading disc element, a cross kneading disc element, a wide kneading disc element, and a progressive mixing screw element.

[0088] The heating temperature during melt-kneading can usually be selected appropriately from the range of 180 to 360°C. If the temperature is too high, decomposition gases are likely to be generated, which may cause extrusion defects such as strand breakage. Therefore, it is desirable to select a screw configuration that takes into account shear heat generation, etc. To suppress decomposition during kneading and subsequent molding processes, it is desirable to use antioxidants and heat stabilizers.

[0089] <Molded products> The molded article of this embodiment is formed from the resin composition of this embodiment or pellets of the resin composition. In this embodiment, the method for producing a molded article is not particularly limited, and any molding method commonly used for resin compositions can be used. Examples include injection molding, ultra-high speed injection molding, injection compression molding, two-color molding, gas-assisted or other hollow molding methods, molding using an insulated mold, molding using a rapidly heated mold, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding), extrusion molding, sheet molding, thermoforming, rotational molding, laminate molding, press molding, and blow molding. A molding method using a hot runner system can also be used.

[0090] The molded article obtained by molding the resin composition of this embodiment is preferably used as a plated molded article having a plated surface. The plating on the molded article of this embodiment is preferably such that it has antenna performance.

[0091] <Method of manufacturing plated molded products> Next, a method for producing a plated molded article will be disclosed, which includes irradiating a laser onto the surface of a molded article formed from the resin composition of this embodiment, and then applying a metal to form a plating. Figure 1 is a schematic diagram showing the process of forming a plating on the surface of a molded article 1 using laser direct structuring technology. In Figure 1, molded article 1 is a flat substrate, but it does not necessarily have to be a flat substrate and may be a molded article with a partially or entirely curved surface. Furthermore, the obtained plated molded article is not limited to final products but also includes various parts.

[0092] Returning to FIG. 1, the molded article 1 is irradiated with a laser 2. The laser here is not particularly limited and can be appropriately selected from known lasers such as a YAG laser, an excimer laser, and electromagnetic rays, with a YAG laser being preferred. The wavelength of the laser is also not particularly limited. A preferred wavelength range is 200 nm to 1200 nm, more preferably 800 to 1200 nm. When the laser is irradiated, the molded article 1 is activated only at the laser-irradiated portion 3. In this activated state, the molded article 1 is applied to a plating solution 4. The plating solution 4 is not particularly specified, and a wide variety of known plating solutions can be used. A plating solution (particularly, an electroless plating solution) containing one or more of copper, nickel, silver, gold, and palladium as the metal component is preferred, a plating solution (particularly, an electroless plating solution) containing one or more of copper, nickel, silver, and gold is more preferred, and a plating solution (particularly, an electroless plating solution) containing copper is even more preferred. That is, in the plating of this embodiment, the metal component is preferably at least one of the above metals. The method for applying the molded article 1 to the plating liquid 4 is not particularly limited, but an example is a method in which the molded article is immersed in a liquid containing the plating liquid. After the plating liquid is applied to the molded article, plating 5 is formed only in the areas that have been irradiated with the laser. The method of this embodiment can form plating (circuits) with intervals of 1 mm or less, or even 150 μm or less (the lower limit is not particularly specified, but for example, 30 μm or more). To prevent corrosion or deterioration of the formed plating (circuits), the plating can be further protected with nickel or gold, for example, after electroless plating. Similarly, electroplating can be used after electroless plating to form a required film thickness in a short time. The method for producing a plated molded article described above is also preferably used as a method for producing a portable electronic device part having an antenna, including the method for producing a plated molded article described above.

[0093] The resin composition, pellets, and molded articles of this embodiment can be used in various applications, such as electronic components (particularly, portable electronic device components) such as connectors, switches, relays, and conductive circuits. In particular, the resin composition, pellets, and molded articles of this embodiment can be preferably used for SMT (Surface Mount Technology) applications.

[0094] In addition, the descriptions in Japanese Patent Application Laid-Open Nos. 2011-219620, 2011-195820, 2011-178873, 2011-168705, and 2011-148267 may be referred to within the scope of the present embodiment. [Example]

[0095] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or the like, measurements can be made using other instruments with equivalent performance.

[0096] 1.Raw materials The following raw materials were used: [Table 1]

[0097] <Synthesis Example of PAPXD10> 8950 g (44.25 mol) of sebacic acid (manufactured by Ito Oil Co., Ltd., product name: Sebacic Acid TA), 12.54 g (0.074 mol) of calcium hypophosphite, and 6.45 g (0.079 mol) of sodium acetate were precisely weighed and charged into a 50-liter reaction vessel equipped with a stirrer, a partial condenser, a cooler, a thermometer, a dropping device, a nitrogen inlet tube, and a strand die. After thoroughly purging the inside of the reaction vessel with nitrogen, it was pressurized to 0.4 MPa with nitrogen, and while stirring, the temperature was raised from 20 °C to 190 °C to uniformly melt sebacic acid in 55 minutes. Then, 5960 g (43.76 mol) of p-xylylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was dropped with stirring over 110 minutes. During this period, the internal temperature of the reaction vessel continuously rose to 293 °C. In the dropping process, the pressure was controlled to 0.42 MPa, and the generated water was removed outside the system through the partial condenser and the cooler. The temperature of the partial condenser was controlled within the range of 145 - 147 °C. After the completion of the dropping of p-xylylenediamine, the polycondensation reaction was continued at an internal pressure of 0.42 MPa in the reaction vessel for 20 minutes. During this period, the internal temperature of the reaction vessel rose to 296 °C. Then, the pressure inside the reaction vessel was reduced from 0.42 MPa to 0.12 MPa over 30 minutes. During this period, the internal temperature rose to 298 °C. Then, the pressure was reduced at a rate of 0.002 MPa / min, and reduced to 0.08 MPa in 20 minutes to adjust the amount of components with a molecular weight of 1,000 or less. The temperature inside the reaction vessel at the completion of the pressure reduction was 301 °C. Then, the system was pressurized with nitrogen, and at a reaction vessel internal temperature of 301 °C and a resin temperature of 301 °C, the polymer was taken out in a strand shape from the strand die and cooled with cooling water at 20 °C, and this was pelletized to obtain about 13 kg of polyamide resin. The cooling time in the cooling water was 5 seconds, and the take-up speed of the strand was 100 m / min. Hereinafter, it is referred to as "PAPXD10". The melting point was 290 °C, and the number average molecular weight was 25,000.

[0098] 2. Examples 1 to 4, Comparative Examples 1 to 5 <Compound> Each component was weighed to obtain the composition shown in Tables 2 and 3, and the components except for the glass fiber were blended in a tumbler. The blend was then fed into the base of a twin-screw extruder (Shibaura Machine Co., Ltd., TEM26SS). After melting, the glass fiber was side-fed to produce pellets. The temperature of the twin-screw extruder was set to 300°C. The components in Tables 2 and 3 are listed in mass%.

[0099] <Flexural strength and flexural modulus> The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours, and then injection-molded into ISO tensile test specimens (4 mm thick) using an injection molding machine (Nissei Plastic Industrial Co., Ltd., "NEX-140III") under conditions of a cylinder temperature of 300°C, a mold temperature of 130°C, and a molding cycle of 50 seconds. The flexural strength (unit: MPa) and flexural modulus (unit: GPa) were measured at a temperature of 23°C in accordance with ISO178.

[0100] <Charpy impact strength> The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours, and then injection-molded into ISO tensile test specimens (4 mm thick) using an injection molding machine (Nissei Plastic Industrial Co., Ltd., "NEX-140III") under conditions of a cylinder temperature of 300°C, a mold temperature of 130°C, and a molding cycle of 50 seconds. Charpy impact strength (notched and unnotched) was measured at a temperature of 23°C according to ISO 179 standard. The unit is kJ / m 2 As shown.

[0101] <Deflection temperature under load (DTUL)> In accordance with ISO75-1 and 2, the deflection temperature under load (unit: °C) was measured using the above ISO tensile test piece (thickness: 4 mm) under a bending stress of 1.80 MPa.

[0102] <Dielectric properties (Dk and Df)> The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours. Then, using an injection molding machine (Nissei Plastic Industrial Co., Ltd., "NEX-140III"), the resin was filled into a 100 x 100 mm, 2 mm thick cavity as a mold at a cylinder temperature of 300°C and a mold temperature of 130°C through a fan gate with a side length of 100 mm and a thickness of 1.5 mm. The gate portion was cut to obtain plate test pieces. The dielectric constant (Dk) and dielectric loss tangent (Df) at 2.45 GHz of the obtained plate specimen were measured using a perturbation method cavity resonator. The perturbation method cavity resonator used was CP-481 manufactured by Kanto Electronics Resistance Development Co., Ltd.

[0103] <Flame retardancy> The polyamide resin pellets obtained by the above-mentioned manufacturing method were dried at 120°C for 4 hours and then injection-molded using an injection molding machine (Shibaura Machine Co., Ltd., "EC-50SXIII") to form UL test specimens measuring 125 mm in length, 13 mm in width, and 0.8 mm in thickness. The cylinder temperature and mold temperature were 300°C and 130°C, respectively. The UL test specimens obtained by the above-mentioned method were conditioned in a thermostatic chamber at a temperature of 23°C and humidity of 50% for 48 hours and subjected to UL94 testing.

[0104] <Plating property - plating growth rate> The pellets obtained by the above-mentioned manufacturing method were dried at 120°C for 4 hours, and then injection molded in an injection molding machine (Nissei Plastic Industrial Co., Ltd., "NEX-140III") under conditions of a cylinder temperature of 300°C, a mold temperature of 130°C, and a molding cycle of 50 seconds to form a plate measuring 60 mm x 60 mm x 2 mm thick. The resulting plate was irradiated with a 1064 nm YAG laser at an output of 10 W, a speed of 80 m / s, and a frequency of 3 μs. The plate was then degreased with a 10 wt% aqueous ethanol solution and plated for 10 minutes in a MacDermid Copper100XB electroless plating bath at 65°C (set temperature: 68°C). The film thickness of the resulting copper plating pattern was measured using a Yamato Scientific FT110 fluorescent X-ray film thickness meter. The plating thickness was calculated from the average value of three arbitrary measurement points. The film thickness of each example and comparative example was expressed as a ratio, with the film thickness of Comparative Example 1 set to 1.0. The larger this value, the faster the plating growth rate. If no plating was formed, it was recorded as ND.

[0105] [Table 2]

[0106] [Table 3]

[0107] In Tables 2 and 3 above, {(C) + (D)} / (B) indicates the mass ratio of the total amount of (B) laser direct structuring additive and (C) phosphorus-based flame retardant to (D) graphite. As is clear from the above results, the resin compositions of the present invention (Examples 1 to 4) can be used as resin compositions for LDS, and when molded into articles, they have excellent flame retardancy, can achieve high dielectric constants while maintaining low dielectric loss tangents, and have high deflection temperatures under load.Furthermore, various mechanical properties are also excellent. In contrast, when the resin composition did not contain graphite, the relative dielectric constant was low when molded into a product (Comparative Example 1). Furthermore, when the resin composition did not contain a phosphorus-based flame retardant (Comparative Example 2), the flame retardancy was poor and plating ability was also somewhat poor when molded into a product. When the resin composition did not contain an LDS additive (Comparative Example 3), the flame retardancy was poor and plating could not be formed when molded into a product. When the resin composition contained a large amount of graphite (Comparative Example 4), the dielectric constant was high and the deflection temperature under load was low when molded into a product. When the resin composition contained a large amount of phosphorus-based flame retardant (Comparative Example 5), the deflection temperature under load was low when molded into a product. [Explanation of symbols]

[0108] 1 Resin molded products 2 Laser 3 Laser irradiated area 4 Plating solution 5. Plating

Claims

1. A resin composition comprising: (A) 10 to 90 mass% of a thermoplastic resin; (B) 1 to 20 mass% of a laser direct structuring additive; (C) 1.0 to 7.9 mass% of a phosphorus-based flame retardant; and (D) 0.3 to 7.0 mass% of graphite, wherein the total of the (A) thermoplastic resin, (B) laser direct structuring additive, (C) phosphorus-based flame retardant, and (D) graphite does not exceed 100 mass%.

2. The resin composition according to claim 1 , wherein the thermoplastic resin (A) comprises a polyamide resin.

3. 2. The resin composition according to claim 1, wherein the thermoplastic resin (A) is composed of diamine-derived structural units and dicarboxylic acid-derived structural units, and the polyamide resin contains 70 mol % or more of the diamine-derived structural units derived from xylylenediamine.

4. The resin composition according to claim 1, wherein the thermoplastic resin (A) comprises a polyamide resin containing diamine-derived structural units and dicarboxylic acid-derived structural units, in which 70 mol % or more of the diamine-derived structural units are derived from paraxylylenediamine, and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from an α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms.

5. The resin composition according to claim 1 or 2, wherein the (D) graphite is in a flake form.

6. 3. The resin composition according to claim 1, wherein {(C) + (D)} / (B), which is the mass ratio of the total amount of the laser direct structuring additive (B) and the phosphorus-based flame retardant (C) to the graphite (D) contained in the resin composition, is less than 1.

00.

7. 3. The resin composition according to claim 1 or 2, further comprising (E) inorganic reinforcing fibers in a proportion of 60% by mass or less, and wherein the total of the (A) thermoplastic resin, (B) laser direct structuring additive, (C) phosphorus-based flame retardant, (D) graphite, and (E) inorganic reinforcing fibers does not exceed 100% by mass.

8. The resin composition according to claim 7 , wherein the (E) inorganic reinforcing fiber includes a glass fiber.

9. The resin composition according to claim 1 or 2, wherein the (C) phosphorus-based flame retardant comprises at least one of a phosphinate and a diphosphinate.

10. The resin composition according to claim 1 or 2, wherein the (C) phosphorus-based flame retardant comprises a phosphinate.

11. The resin composition according to claim 1 or 2, wherein the (B) laser direct structuring additive comprises copper chromium oxide.

12. The resin composition according to claim 1 or 2, further comprising a nucleating agent.

13. the thermoplastic resin (A) comprises a polyamide resin containing diamine-derived structural units and dicarboxylic acid-derived structural units, in which 70 mol % or more of the diamine-derived structural units are derived from paraxylylenediamine, and 70 mol % or more of the dicarboxylic acid-derived structural units are derived from an α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms; The (D) graphite is in a flake form, the mass ratio of the {(C) phosphorus-based flame retardant + (D) graphite} / (B) laser direct structuring additive is less than 1; Furthermore, (E) inorganic reinforcing fibers are 60% by mass or less, and the total of the (A) thermoplastic resin, (B) laser direct structuring additive, (C) phosphorus-based flame retardant, (D) graphite, and (E) inorganic reinforcing fibers does not exceed 100% by mass, The (E) inorganic reinforcing fiber contains glass fiber, the (C) phosphorus-based flame retardant contains a phosphinate, the (B) laser direct structuring additive contains copper chromium oxide; The resin composition of claim 1 , further comprising a nucleating agent.

14. A molded article formed from the resin composition according to claim 1, 2 or 13.

15. The molded article according to claim 14, wherein the surface of the molded article is plated.

16. The molded article according to claim 15, wherein the plating has antenna properties.

17. The molded article according to claim 14, which is a portable electronic device part.

18. A method for producing a plated molded article, comprising irradiating a surface of a molded article formed from the resin composition according to claim 1 with a laser and then applying a metal to form a plating.

19. Pellets of the resin composition according to claim 1, 2 or 13.

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