Flame-retardant resin composition for laser direct structuring, resin molded products, and high-frequency antenna-related components

Abstract

To provide a resin composition for flame retardant laser direct structuring which has high flame retardancy, in addition to low dielectric characteristics, plating property and strength.SOLUTION: A resin composition for flame retardant laser direct structuring contains (a) a polyphenylene ether-based resin, (b) 1,3-phenylene bis(1,3 dixylylene phosphate), (c) a glass fiber, and (d) a laser direct structuring additive, wherein with respect to 100 mass% of the total of the components (a) to (d), a content ratio of the component (a) is 40 to 80 mass%, a content ratio of the component (b) is 10 to 25 mass%, a content ratio of the component (c) is 5 to 20 mass%, and a content ratio of the component (d) is 5 to 15 mass%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a flame-retardant resin composition for laser direct structuring, a resin molded article, and a high-frequency antenna-related member. [Background technology]

[0002] In recent years, MID (molded interconnect device) technology, which directly attaches an antenna to a resin molded body, has been used as a communication antenna for mobile devices such as smartphones. Among these, LDS (laser direct structuring), a type of MID technology, has been attracting particular attention as a technique that can easily create circuits on the surface of a resin molded body using laser irradiation technology. This is a technique in which a specific metal oxide is added to the material in advance, and the metal oxide is activated by irradiating the molded body with a laser at the location where the circuit is to be created, followed by metal plating, with plating only being applied to the laser-irradiated areas. (See, for example, Patent Documents 1 to 4.)

[0003] In recent years, there has been a demand for materials used in the LDS method to have even higher flame retardancy. To meet this demand, a technique using a specific phosphorus-based flame retardant has been disclosed (see, for example, Patent Documents 3 and 4). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-144767 [Patent Document 2] Japanese Patent Publication No. 2022-157658 [Patent Document 3] Japanese Patent Application Publication No. 2020-515659 [Patent Document 4] WO2019 / 180592 Summary of the Invention [Problem to be solved by the invention]

[0005] As the use of LDS technology as described above spreads, communication frequencies will become higher in 5G and later communication standards, which require materials that are superior to conventional materials in terms of low dielectric properties, plating properties, and strength, as well as high flame retardancy. To address environmental concerns, non-halogen flame retardants, especially phosphorus-based flame retardants, are commonly used to make resin compositions flame-retardant. However, the inventors' research has revealed that although resin compositions containing LDS additives can improve flame retardancy, their dielectric properties and fluidity may be impaired.

[0006] The present invention has an object to solve the above problems, and provides a resin material that has low dielectric properties, plating properties, strength, and also high flame retardancy. [Means for solving the problem]

[0007] As a result of intensive research to solve the above problems, the inventors have found that the above problems can be solved by adding a specific phosphorus-based flame retardant in a specific ratio together with an LDS additive, and have thus completed the present invention.

[0008] That is, the present invention is as follows. [1] (a) a polyphenylene ether resin; (b) 1,3-phenylenebis(1,3 dixylylene phosphate), (c) glass fibers; (d) a laser direct structuring additive; A flame-retardant resin composition for laser direct structuring, characterized in that, relative to 100% by mass of the total of the components (a) to (d), the content ratio of the component (a) is 40 to 80% by mass, the content ratio of the component (b) is 10 to 25% by mass, the content ratio of the component (c) is 5 to 20% by mass, and the content ratio of the component (d) is 5 to 15% by mass. [2] The resin composition according to [1], wherein the weight-average molecular weight of the (a) polyphenylene ether resin is 35,000 to 60,000. [3] The resin composition according to [1] or [2], wherein the laser direct structuring additive contains chromium copper oxide and / or an oxide containing antimony and tin. [4] A resin molded article formed from the resin composition according to any one of [1] to [3]. [5] The resin molded product according to [4], characterized in that the surface of the resin molded product is plated. [6] A high-frequency antenna-related component, comprising the resin molded product according to [4] or [5]. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a resin composition, a resin molded article, and a high-frequency antenna-related member that have low dielectric properties, plating properties, strength, and high flame retardancy. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. The present invention is not limited to the following embodiment, and various modifications can be made within the scope of the gist thereof.

[0011] [Flame-retardant resin composition for laser direct structuring] The flame-retardant resin composition for laser direct structuring of this embodiment (hereinafter sometimes referred to as the "resin composition of this embodiment") has the following properties: (a) a polyphenylene ether resin (component (a)); (b) 1,3-phenylenebis(1,3-dixylylene phosphate (component (b))), (c) glass fiber ((c) component); (d) a laser direct structuring additive ((d) component); Includes.

[0012] In the resin composition of this embodiment, the content of the component (a) is 40 to 80 mass%, the content of the component (b) is 10 to 25 mass%, the content of the component (c) is 5 to 20 mass%, and the content of the component (d) is 5 to 15 mass%, relative to 100 mass% of the total of the components (a) to (d). In the resin composition of this embodiment, by ensuring that the content ratio of each component relative to the total of 100 mass% of the components (a) to (d) is within the above range, an excellent balance of physical properties can be achieved in terms of low dielectric characteristics, plating properties, and flame retardancy.

[0013] The components of the resin composition of this embodiment will be described below. ((a) Polyphenylene ether resin) The resin composition of the present embodiment contains a polyphenylene ether resin (hereinafter, sometimes simply referred to as "PPE resin") as component (a). Because the resin composition of the present embodiment contains a polyphenylene ether resin, the resin composition of the present embodiment has excellent heat resistance.

[0014] The PPE resin is preferably a resin made only of polyphenylene ether (hereinafter, sometimes referred to as "PPE"), but may also be a mixed resin made of PPE and polystyrene resin. Since the PPE resin contains PPE, the heat resistance is even more excellent.

[0015] Examples of the PPE include a homopolymer having a repeating unit structure represented by the following formula (1) and a copolymer having a repeating unit structure represented by the following formula (1). The PPE may be used alone or in combination of two or more. [ka] In the above formula (1), R 1 , R 2 , R 3 , and R 4are each independently a monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, a secondary alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, and a halohydrocarbonoxy group in which at least two carbon atoms separate the halogen atom from the oxygen atom.

[0016] From the viewpoint of fluidity, toughness, and chemical resistance during processing, the PPE preferably has a reduced viscosity of 0.15 to 2.0 dL / g, more preferably 0.20 to 1.0 dL / g, and even more preferably 0.30 to 0.70 dL / g, as measured using a 0.5 g / dL chloroform solution at 30°C with an Ubbelohde viscometer.

[0017] Examples of the PPE include, but are not limited to, homopolymers such as poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), and poly(2,6-dichloro-1,4-phenylene ether); and copolymers such as copolymers of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol). Among these, from the viewpoints of the balance between toughness and rigidity when made into a resin composition and the ease of obtaining raw materials, poly(2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred, and poly(2,6-dimethyl-1,4-phenylene ether) is more preferred.

[0018] The PPE can be produced by known methods, including, but not limited to, the oxidative polymerization of 2,6-xylenol by Hay using a complex of cuprous salt and amine as a catalyst, as described in U.S. Pat. No. 3,306,874, and the methods described in U.S. Pat. Nos. 3,306,875, 3,257,357, 3,257,358, JP-B-52-17880, JP-A-50-51197, and JP-A-63-152628.

[0019] The PPE may be a modified PPE obtained by reacting the homopolymer and / or copolymer with a styrene-based monomer or a derivative thereof, and / or an α,β-unsaturated carboxylic acid or a derivative thereof, wherein the graft or addition amount of the styrene-based monomer or a derivative thereof and / or the α,β-unsaturated carboxylic acid or a derivative thereof is preferably 0.01 to 10% by mass relative to 100% by mass of the component (a).

[0020] Examples of methods for producing the modified PPE include a method in which the PPE is reacted in the presence or absence of a radical generator in a molten state, solution state, or slurry state at a temperature of 80 to 350°C.

[0021] The PPE may be a mixture of the homopolymer and / or copolymer and the modified PPE in any ratio.

[0022] The weight average molecular weight of the (a) polyphenylene ether resin is preferably 35,000 to 60,000. From the viewpoints of impact resistance and flame retardancy, the weight average molecular weight is preferably 35,000 or more, and from the viewpoint of flowability, it is preferably 60,000 or less. The weight average molecular weight of (a) polyphenylene ether resin was measured using a gel permeation chromatography system 21 manufactured by Showa Denko K.K. (column: one KG, one K-800RL, and one K-800R connected in series, column temperature: 40 ° C, solvent: chloroform, solvent flow rate: 10 mL / min, sample concentration: 1 g / L chloroform solution of hydrogenated block copolymer) using standard polystyrene. The UV (ultraviolet) wavelength of the detector was set to 254 nm to create a calibration curve. Then, the weight average molecular weight of (a) polyphenylene ether resin was measured by setting the wavelength of the UV (ultraviolet) of the detector to 283 nm.

[0023] Examples of the polystyrene resin contained in the component (a) include atactic polystyrene, rubber-reinforced polystyrene (high impact polystyrene, HIPS), styrene-acrylonitrile copolymer (AS) having a styrene content of 50% by weight or more, and AS resin in which the styrene-acrylonitrile copolymer is rubber-reinforced, and atactic polystyrene and / or high impact polystyrene are preferred. The polystyrene resins may be used alone or in combination of two or more.

[0024] In addition, in the component (a), the mass ratio of PPE to polystyrene resin (PPE / polystyrene resin) is preferably 60 / 40 to 100 / 0, and more preferably 80 / 20 to 100 / 0, from the viewpoint of flame retardancy and heat resistance.

[0025] From the viewpoints of flame retardancy and heat resistance, the content of the component (a) in the resin composition of this embodiment is 40 to 80% by mass when the total amount of the components (a) to (d) is 100% by mass. If the content ratio of the component (a) to the total amount of the components (a) to (d) is in the range of 40 to 80% by mass, a sufficiently good balance between flame retardancy and heat resistance can be achieved. From the same viewpoint, the content ratio of the component (a) to the total amount of the components (a) to (d) is preferably 50 to 80% by mass.

[0026] ((b) 1,3-phenylenebis(1,3 dixylylene phosphate)) The resin composition of the present embodiment contains 1,3-phenylenebis(1,3 dixylylene phosphate) as the component (b). In the resin composition of this embodiment, the heat resistance and flame retardancy improving effect of the polyphenylene ether resin of component (a) and the flame retardancy improving effect of the 1,3-phenylenebis(1,3 dixylylene phosphate) of component (b) are combined to significantly improve the flame retardancy.

[0027] In addition to the component (b) described above, the resin composition of the present embodiment may also contain other flame retardant components as needed, to the extent that the plating properties, dielectric properties, fluidity, heat resistance, impact resistance, and flame retardancy of the resin composition are not impaired. Examples of other flame retardant components include, but are not limited to, organic phosphate ester compounds, metal phosphinate compounds, ammonium polyphosphate compounds, silicone flame retardants, and phosphazene flame retardants. Of these, it is preferable to use organic phosphate ester compounds, and particularly aromatic condensed phosphate ester flame retardants.

[0028] In the resin composition of this embodiment, the content of the component (b) is 10 to 25% by mass, based on 100% by mass of the total of the components (a) to (d), from the viewpoints of flame retardancy and heat resistance. If the content ratio of the component (b) relative to 100% by mass of the total of the components (a) to (d) is in the range of 10 to 25% by mass, a sufficiently good balance between flame retardancy and heat resistance can be achieved. From the same viewpoint, the content ratio of the component (b) relative to the total of the components (a) to (d) is preferably 13 to 22% by mass.

[0029] (c) Glass fiber The resin composition of the present embodiment contains glass fibers as component (c). Known glass fibers can be used as the glass fibers. The glass fibers are preferably surface-treated to improve adhesion to the resin. Examples of the surface treatment include treatment with various coupling agents such as silane-based and titanate-based coupling agents, and among these, it is preferable to use glass fibers to which aminosilane and epoxysilane-based coupling agents have been added.

[0030] From the viewpoint of the reinforcing effect, the glass fibers preferably have an L / D, which is the ratio of the average diameter (D) of the fibers to the average length (L), of 5 or more.

[0031] The glass fibers may be obtained by melt spinning commonly available glass such as E-glass, C-glass, A-glass, S-glass, D-glass, R-glass, and alkali-resistant glass. Preferred examples of the present embodiment include D-glass and E-glass, and among these, E-glass is particularly preferred.

[0032] Furthermore, the glass fiber is 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 attached is preferably 0.01 to 1 mass% of the glass fiber. If necessary, the glass fiber 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 resin capable of forming a film, such as an epoxy resin or urethane resin, or a mixture of a resin capable of forming a film with a heat stabilizer or a flame retardant.

[0033] From the viewpoints of plating ability, heat resistance, impact resistance, and flame retardancy, the content of the component (c) in the resin composition of this embodiment is 5 to 20 mass% relative to 100 mass% of the total amount of the components (a) to (d). If the content ratio of the component (c) relative to the total amount of the components (a) to (d) is in the range of 5 to 20 mass%, a sufficiently good balance between plating ability and flame retardancy can be achieved. From the same viewpoint, the content ratio of the component (c) relative to the total amount of the components (a) to (d) is preferably 5 to 12 mass%, more preferably 6 to 12 mass%.

[0034] ((d) Laser Direct Structuring Additive) The resin composition of the present embodiment contains a laser direct structuring additive (hereinafter, also referred to as "LDS additive") as component (d). The inclusion of an LDS additive makes it possible to form a plating on the resulting resin molded article. The LDS additive may be a synthetic product or a commercially available product. Regarding the commercially available product, in addition to those commercially available as LDS additives, substances sold for other uses may also be used as long as they satisfy the requirements of the LDS additive of this embodiment. The LDS additive may be used alone or in combination of two or more types.

[0035] The LDS additive preferably contains at least one of copper, antimony, tin, aluminum, and zinc, more preferably contains copper chromium oxide and / or an oxide containing antimony and tin, and even more preferably contains an oxide containing at least antimony and tin.

[0036] Specifically, a first embodiment of the LDS additive is a compound containing copper and chromium. The LDS additive of the first embodiment preferably contains 10 to 30 mass% of copper and 15 to 50 mass% of chromium. The LDS additive of the first embodiment is preferably an oxide containing copper and chromium (copper chromium oxide).

[0037] The copper and chromium are preferably contained in a spinel structure, which is one of the typical crystal structures found in AB2O4 type compounds (A and B are metal elements) in double oxides.

[0038] 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.

[0039] A second embodiment of the LDS additive is an oxide containing at least one of antimony and phosphorus and tin, preferably an oxide containing antimony and tin. In the LDS additive of the second embodiment, the tin content is more preferably greater than the phosphorus and antimony contents, and the amount of tin relative to the total amount of tin, phosphorus, and antimony is more preferably 80 mass % or more.

[0040] 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. 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, with antimony oxide-doped tin oxide and antimony oxide-doped tin oxide being preferred, and antimony oxide-doped tin oxide being more preferred.

[0041] The number average particle size of the LDS additive 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 formed on the molded article can be made more uniform.

[0042] From the viewpoint of plating properties, the content of the component (d) in the resin composition of this embodiment is preferably 5 to 15 mass% relative to 100 mass% of the total amount of the components (a) to (d). If the content ratio of the component (d) relative to 100 mass% of the total amount of the components (a) to (d) is in the range of 5 to 15 mass%, a sufficiently good balance between plating properties and flame retardancy can be achieved. From the same viewpoint, the content ratio of the component (d) relative to 100 mass% of the total amount of the components (a) to (d) is preferably 5 to 12 mass%, more preferably 6 to 12 mass%.

[0043] The resin composition of the present embodiment may contain only one type of LDS additive or two or more types. When two or more types are contained, the total amount of the LDS additives is preferably within the above-mentioned range.

[0044] (Other ingredients) In addition to the components (a) to (d) described above, the resin composition of the present embodiment may contain other components as needed, within a range that does not impair the plating properties, thermal conductivity, electrical resistance, fluidity, low volatile content, heat resistance, and flame retardancy of the resin composition.

[0045] Examples of the other components include, but are not limited to, thermoplastic elastomers (block copolymers, polyolefin elastomers, etc.), heat stabilizers, antioxidants, metal deactivators, crystal nucleating agents, flame retardants (organic phosphate ester compounds, ammonium polyphosphate compounds, silicone flame retardants, phosphazene flame retardants, metal phosphinates, etc.), plasticizers (low-molecular-weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), weather (light) resistance improvers, slip agents, inorganic or organic fillers or reinforcing materials (carbon fibers, polyacrylonitrile fibers, aramid fibers, etc.), various colorants, and mold release agents.

[0046] [Method for producing resin composition] The resin composition of this embodiment can be produced by melt-kneading components (a) to (d), and, if necessary, other components.

[0047] The melt kneader used for melt kneading is not limited to, but includes, for example, a single-screw extruder, a multi-screw extruder including a twin-screw extruder, a roll, a kneader, a Brabender Plastograph, a Banbury mixer, etc., and from the viewpoint of kneading properties, a twin-screw extruder is particularly preferred. Specific examples include the ZSK series manufactured by Werner & Pfleiderer, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by The Japan Steel Works, Ltd.

[0048] An example of a preferred production method using an extruder will be described below. The L / D (effective barrel length / inner barrel diameter) of the extruder is preferably 20 or more and 60 or less, and more preferably 30 or more and 50 or less. The configuration of the extruder is not particularly limited, but for example, it is preferable to have a first raw material supply port on the upstream side of the flow direction of the raw materials, a first vacuum vent downstream of the first raw material supply port, a second raw material supply port 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), and a second vacuum vent downstream of the second raw material supply port.In particular, it is more preferable to have a kneading section upstream of the first vacuum vent, a kneading section between the first vacuum vent and the second raw material supply port, a kneading section between the second to fourth raw material supply ports and the second vacuum vent, and a kneading section between the second to fourth raw material supply ports and the second vacuum vent.

[0049] The method of supplying raw materials to the second to fourth raw material supply ports is not particularly limited, but a method of supplying raw materials from the side open port of the extruder using a forced side feeder is preferred because it tends to provide more stable supply than a method of simply adding raw materials through the open ports of the second to fourth raw material supply ports of the extruder.

[0050] In particular, when the raw materials contain powder and it is desired to reduce the generation of crosslinked products or carbonized products due to the thermal history of the resin, a method using a forced side feeder that supplies the raw materials from the side of the extruder is more preferable, and a method in which forced side feeders are provided at the second to fourth raw material supply ports and the raw material powders are supplied in portions is even more preferable.

[0051] When adding a liquid raw material, it is preferable to add it into the extruder using a plunger pump, gear pump or the like.

[0052] The upper openings of the second to fourth raw material supply ports of the extruder can also be used as openings for venting the air being transported. The melt-kneading temperature and screw rotation speed in the melt-kneading step of the resin composition are not particularly limited, but can be selected so that the resin can be heated and melted without difficulty and processed at a temperature equal to or higher than the melting point of the crystalline resin for the crystalline resin, or at a temperature equal to or higher than the glass transition temperature of the amorphous resin for the amorphous resin. Typically, the temperature is selected arbitrarily from 200 to 370°C, and the screw rotation speed is 100 to 1200 rpm.

[0053] One specific example of a method for producing the resin composition of this embodiment using a twin-screw extruder is to supply the polyphenylene ether resin (a) and 1,3-phenylenebis(1,3 dixylylene phosphate) (b) to the first raw material supply port of the twin-screw extruder, set the heat melting zone to the melting temperature of the polyphenylene ether resin, and melt-knead them at a screw rotation speed of 100 to 1200 rpm, preferably 200 to 500 rpm, and then add the LDS additive (d) through the second raw material supply port and the glass fiber (c) through the third raw material supply port to the molten resin, followed by melt-kneading. Furthermore, the positions at which the components (a) to (d) are supplied to the twin-screw extruder may be such that the second and third raw material supply ports are provided as described above, and each component may be supplied separately, or all components may be supplied collectively through the first raw material supply port of the extruder.

[0054] Furthermore, when reducing the generation of crosslinked products or carbonized materials due to the thermal history of the resin in the presence of oxygen, it is preferable to maintain the oxygen concentration of each process line in the route of adding each raw material to the extruder at less than 1.0% by volume. The adding route is not particularly limited, but a specific example can include a configuration in which, in order from a stock tank, there is a pipe, a gravimetric feeder with a refill tank, another pipe, a supply hopper, and a twin-screw extruder. A method for maintaining such a low oxygen concentration is not particularly limited, but an effective method is to introduce an inert gas into each process line with increased airtightness. Usually, nitrogen gas is introduced to remove oxygen. It is preferred to keep the concentration below 1.0% by volume.

[0055] When the polyphenylene ether resin of component (a) contains a powdery component (having a volume average particle size of less than 10 μm), the above-described method for producing a resin composition has the effect of further reducing residues in the screws of a twin-screw extruder when the resin composition of the present embodiment is produced using a twin-screw extruder, and further has the effect of reducing the generation of black spots, carbonized matter, and the like in the resin composition obtained by the above-described production method.

[0056] As a specific method for producing the resin composition of this embodiment, it is preferable to use an extruder in which the oxygen concentration at each raw material supply port is controlled to less than 1.0% by volume, and to carry out any one of the following methods 1 to 3. 1. A production method comprising melt-kneading the components (a) and (b) contained in the resin composition of this embodiment (first kneading step), supplying the component (d) to the molten mixture obtained in the first kneading step, followed by melt-kneading (second kneading step), and supplying the entire amount of the component (c) to the molten mixture obtained in the second kneading step, followed by melt-kneading (third kneading step). 2. A production method comprising melt-kneading all of the components (a) to (c) contained in the resin composition of this embodiment (first kneading step), supplying all of the component (d) to the molten mixture obtained in the first kneading step, and subsequently melt-kneading the mixture (second kneading step). 3. A method of melt-kneading all of the components (a) to (d) contained in the resin composition of this embodiment.

[0057] In particular, the raw materials for component (a), polyphenylene ether, component (b), 1,3-phenylenebis(1,3 dixylylene phosphate), and component (d), LDS agent, are in powder form, while phosphate ester flame retardants are sometimes liquid, making them difficult to fit into the extruder, making it difficult to increase production volume per hour, and increasing the resin's residence time in the extruder, making them prone to thermal degradation.Furthermore, component (c), glass fiber, is relatively prone to breaking. Therefore, the resin composition obtained by the manufacturing method 1 is more suitable than the resin compositions obtained by the manufacturing methods 2 and 3 in that it has excellent mixability of the components, can reduce decomposition due to thermal degradation and the generation of crosslinked products and carbonized products, can reduce breakage of glass fibers, and can increase the amount of resin produced per unit time, thereby providing a resin composition with excellent productivity and quality.

[0058] [Resin molded product] The resin molded article of this embodiment is a resin molded article formed from the resin composition of this embodiment described above. In this embodiment, the method for producing a resin molded product 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.

[0059] Furthermore, depending on the application of the product, the resin molded article of this embodiment may preferably have a plating on the surface of the resin molded article. By plating the surface, performance such as corrosion resistance can be further improved. The type of plating is not particularly limited and can be selected appropriately depending on the required performance. The resin molded article of this embodiment has excellent plating properties, so the quality of the plating applied to the surface is good.

[0060] The resin molded article of this embodiment can be used as a high-frequency antenna-related member (for example, an antenna or a pendulum).The molded article can also be widely used as an optical device mechanism part, a light source lamp peripheral part, a metal film laminate substrate sheet or film, an internal part of a hard disk, an optical fiber connector ferrule, a printer part, a copy machine part, a water pump / piping part, an automobile engine room part such as an automobile radiator tank part, an automobile lamp part, etc. [Example]

[0061] Hereinafter, the present embodiment will be described with reference to specific examples and comparative examples, but the present embodiment is not limited to these.

[0062] The raw materials used in the examples and comparative examples are shown below. <Component (a): Polyphenylene ether resin> (a1): PPE (polyphenylene ether) Polyphenylene ether (weight average molecular weight 30,000) obtained by oxidative polymerization of 2,6-xylenol. (a2): PPE (polyphenylene ether) Polyphenylene ether (weight average molecular weight 35,000) obtained by oxidative polymerization of 2,6-xylenol. (a3): PPE (polyphenylene ether) Polyphenylene ether (weight average molecular weight 60,000) obtained by oxidative polymerization of 2,6-xylenol. (a4): PPE (polyphenylene ether) Polyphenylene ether (weight average molecular weight 70,000) obtained by oxidative polymerization of 2,6-xylenol. (a5): High impact polystyrene (Polystyrene CT60: manufactured by Petrochemicals Co., Ltd.).

[0063] <Component (b): 1,3-phenylenebis(1,3-dixylylene phosphate)> (b1) 1,3-phenylenebis(1,3 dixylylene phosphate) PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.)

[0064] <(c) Component: Glass fiber> (c1) E-glass fiber with an average diameter of 13 μm and surface treatment with an aminosilane coupling agent. Mohs hardness: 6.5.

[0065] <(d) Component: LDS additive> (d1) Copper chromium oxide LD14 (manufactured by Shepherd Color Company). Mohs hardness 5.5. (d2) Tin-antimony composite oxide CP05 (manufactured by Keeling & Walker Limited). Mohs hardness: 6.5.

[0066] <(e) Other ingredients> (e1) CR-741 (manufactured by Daihachi Chemical Industry Co., Ltd.) (e2) EXOLIT OP1230 (Clariant Co., Ltd.)

[0067] [Examples 1 to 10, Comparative Examples 1 to 8] The resin compositions to be used as samples were produced using a twin-screw extruder ZSK-40 (manufactured by Coperion). In this twin-screw extruder, a first raw material supply port was provided upstream of the flow direction of the raw materials, and a first vacuum vent, a second raw material supply port, a third raw material supply port (liquid addition nozzle), and a fourth raw material supply port were provided downstream of this, and a second vacuum vent was provided further downstream of these. Using the extruder set up as described above, components (a) to (d) were added according to the compositions shown in Tables 1 and 2, and melt-kneaded at an extrusion temperature of 270 to 320°C, a screw rotation speed of 300 rpm, and a discharge rate of 100 kg / hour to produce pellets. Pellets of this resin composition were fed into a screw in-line injection molding machine set at a cylinder temperature of 280°C and a mold temperature of 80°C, and a test piece Type A was molded in accordance with ISO 10724-1. The deflection temperature under load (in accordance with JIS K7191-1) was measured using this test piece. The above-mentioned production conditions and measurement results are shown in Tables 1 and 2. The amounts of components (a) to (d) added in the table are percentages relative to the total amount of components (a) to (d), which is 100% by mass.

[0068] 〔evaluation〕 The methods for measuring and evaluating the physical properties obtained in each of the Examples and Comparative Examples are shown below. (1) Flame retardancy The test was carried out in accordance with the vertical flame test method of UL94 (a standard established by Underwriters Laboratories Inc., USA). The results are shown in Tables 1 and 2.

[0069] (2) Plating The resulting resin composition pellets were fed into a small injection molding machine (product name: EC75-SX2, manufactured by Shibaura Machine Co., Ltd.) with a cylinder temperature set to 280-320°C. A 60mm x 60mm x 2.0mm plate was fabricated under the following conditions: mold temperature 80°C, injection pressure 100MPa, injection time 15 seconds, and cooling time 20 seconds. The plate was activated using a laser irradiator (product name "Micro Line 3D16 0", manufactured by LPKF). It was then plated in an electroless copper plating bath (product name "MID copper 100B1", manufactured by McDermid) at 57°C for 45 minutes. Plating performance was evaluated visually by the thickness of the plated copper according to the following criteria. The results are shown in Tables 1 and 2. ◎ (Excellent): The copper color is deep and the plating is thick. 〇 (Good): Plating is on but a little thin × (bad): No plating at all

[0070] (3) Dielectric properties (relative permittivity, dielectric loss tangent) The obtained resin composition pellets were fed into a small injection molding machine (product name: EC75-SX2, manufactured by Shibaura Machine Co., Ltd.) with a cylinder temperature set to 280 to 320°C, and a 55 mm x 55 mm x 0.9 mm flat plate 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, and the dielectric constant and dielectric loss tangent were measured under the conditions below. The test pieces were left to stand in an atmosphere of 23°C and 50% RH for at least 24 hours, and then the dielectric constant (Dk) and dielectric loss tangent (Df) were measured under the following conditions using a network analyzer (model: N5224B, Keysight Technologies) in an atmosphere of 23°C and 50% RH. The dielectric constant and dielectric loss tangent were calculated from the average values ​​of three test pieces. The results are shown in Tables 1 and 2. The lower these values, the better the dielectric properties. Resonator: Split-post dielectric resonator (model: N1501AE10, Keysight Technologies) Frequency: 10GHz

[0071] (4) Liquidity MFR was measured in accordance with JIS-K7210 at a temperature of 250°C and a load of 5 kg. The results are shown in Tables 1 and 2.

[0072] (5) Heat resistance The deflection temperature under load (°C) of the thermoplastic resin compositions obtained in the examples and comparative examples described below was measured in accordance with JIS K7191-1. The results are shown in Tables 1 and 2. The higher the measured value, the better the heat resistance was evaluated to be.

[0073] [Table 1]

[0074] [Table 2]

[0075] As shown in Tables 1 and 2, the resin compositions obtained in Examples 1 to 10 were found to be excellent in flame retardancy, plating properties, and dielectric properties, as well as in the balance between fluidity and heat resistance. On the other hand, the resin compositions obtained in Comparative Examples 1 to 8 were comparable in flame retardancy, plating property, and dielectric properties to those of the Examples, but were inferior in either fluidity or heat resistance, resulting in a balance inferior to the resin compositions obtained in each Example. [Industrial Applicability]

[0076] The thermoplastic resin composition of this embodiment has excellent flame retardancy, plating properties, and dielectric properties, as well as fluidity, heat resistance, and impact resistance, thereby increasing the design freedom of resin molded products. Therefore, it can be used as various parts in electrical and electronic devices, automotive equipment, chemical equipment, optical equipment, and antennas. For example, it has industrial applicability in chassis and cabinets for digital versatile disks and the like, optical device mechanical parts such as optical pickup slide bases, light source lamp peripheral parts, metal film laminate substrate sheets or films, hard disk internal parts, optical fiber connector ferrules, laser beam printer internal parts (toner cartridges, etc.), inkjet printer internal parts, copier internal parts, water pump and piping components, automobile engine room internal parts such as automobile radiator tank parts, automobile lamp parts, and high-frequency antenna-related components.

Claims

1. (a) a polyphenylene ether resin; (b) 1,3-phenylenebis(1,3 dixylylene phosphate); (c) glass fibers; (d) a laser direct structuring additive; A flame-retardant resin composition for laser direct structuring, characterized in that, relative to 100% by mass of the total of the components (a) to (d), the content ratio of the component (a) is 40 to 80% by mass, the content ratio of the component (b) is 10 to 25% by mass, the content ratio of the component (c) is 5 to 20% by mass, and the content ratio of the component (d) is 5 to 15% by mass.

2. 2. The resin composition according to claim 1, wherein the weight average molecular weight of the polyphenylene ether resin (a) is 35,000 to 60,000.

3. 3. The resin composition according to claim 1, wherein the laser direct structuring additive comprises chromium copper oxide and / or an oxide containing antimony and tin.

4. A resin molded product formed from the resin composition according to claim 1 or 2.

5. 5. The resin molded product according to claim 4, wherein the surface of the resin molded product is plated.

6. A high frequency antenna-related member comprising the resin molded product according to claim 4.

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