JP6239960B2 - Thermoplastic resin composition for laser direct structuring, resin molded product, and method for producing resin molded product - Google Patents

Description

  The present invention relates to a thermoplastic resin composition for laser direct structuring. Furthermore, it is related with the manufacturing method of the resin molded product formed by shape | molding the said thermoplastic resin composition, and the resin molded product with a plating layer which formed the plating layer on the surface of the said resin molded product.

  In recent years, with the development of mobile phones including smartphones, various methods for manufacturing antennas inside mobile phones have been studied. In particular, there is a need for a method of manufacturing an antenna that can be three-dimensionally designed for a mobile phone. As one of the techniques for forming such a three-dimensional antenna, a laser direct structuring (hereinafter, also referred to as “LDS”) technique has attracted attention. LDS technology, for example, irradiates the surface of a resin molded product containing an LDS additive with a laser, activates only the portion irradiated with the laser, and forms a plating layer by applying metal to the activated portion. Technology. A feature of this technique is that a metal structure such as an antenna can be manufactured directly on the surface of the resin base material without using an adhesive or the like. Such LDS technology is disclosed in, for example, Patent Documents 1 to 4 and the like.

International publication WO2011 / 095632 pamphlet International Publication WO2011 / 076729 Pamphlet International Publication WO2011 / 077630 Pamphlet International Publication WO2012 / 128219 Pamphlet

Here, in recent years, it is required to impart thermal conductivity also to the thermoplastic resin composition for LDS. In order to impart thermal conductivity to a thermoplastic resin composition, generally, a thermal conductive filler or the like is blended into the thermoplastic resin composition. However, in the thermoplastic resin composition for LDS containing the LDS additive containing antimony and tin, since the LDS additive is a white color, an attempt to make use of the characteristics of the white color will result in a black color. It is not desirable to use a thermally conductive filler. Therefore, it is conceivable to mix boron nitride as the heat conductive material. However, in order to maintain plating properties while providing sufficient thermal conductivity with boron nitride, it is necessary to add a large amount of boron nitride and LDS additive, and the resin component in the thermoplastic resin composition is relatively small. turn into. As a result, the ratio of the inorganic substance in the thermoplastic resin composition increases, resulting in poor mechanical strength or poor fluidity of the resin composition.
The present invention aims to solve such problems, and provides a thermoplastic resin composition having excellent thermal conductivity, capable of forming an appropriate plating, and having excellent mechanical strength and fluidity. The purpose is to do.

  Under such circumstances, the inventors of the present application have conducted intensive studies. As a result, in a thermoplastic resin composition containing a polycarbonate resin, an LDS additive containing antimony and tin, and boron nitride, the LDS additive and boron nitride are blended. It has been found that the above problem can be solved by setting the ratio within a predetermined range. Specifically, the above problem has been solved by the following means <1>, preferably <2> to <14>.

<1> 5 to 20 parts by weight of a laser direct structuring additive and 30 to 60 parts by weight of boron nitride with respect to 100 parts by weight of a resin component containing 60 to 100% by weight of a polycarbonate resin and 40 to 0% by weight of a styrene resin And 10-50 parts by weight of glass fiber, the laser direct structuring additive contains antimony and tin, and the weight ratio of the laser direct structuring additive to boron nitride (boron nitride / laser direct structuring additive) is The thermoplastic resin composition for laser direct structuring which is 2-7.
<2> The thermoplastic resin composition for laser direct structuring according to <1>, wherein the styrene-based resin is an acrylonitrile-butadiene-styrene copolymer.
<3> The thermoplastic resin composition for laser direct structuring according to <1> or <2>, further comprising an elastomer.
<4> The elastomer comprises at least one rubber component selected from polybutadiene-containing rubber, polybutylacrylate-containing rubber, polyorganosiloxane rubber, and IPN composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber. The thermoplastic resin for laser direct structuring according to <3>, which is a core / shell type graft copolymer having a layer and a shell layer formed by copolymerizing (meth) acrylic acid ester in the core layer Composition.
<5> The thermoplastic resin composition for laser direct structuring according to any one of <1> to <4>, wherein the metal component included in the laser direct structuring additive is tin in the largest amount. .
<6> The thermoplastic resin composition for laser direct structuring according to any one of <1> to <5>, further comprising a phosphorus-based stabilizer and / or an antioxidant.
<7> A resin molded product formed by molding the thermoplastic resin composition for laser direct structuring according to any one of <1> to <6>.
<8> The resin molded product according to <7>, further having a plating layer on the surface.
<9> The resin molded product according to <7> or <8>, which is a mechanical component.
<10> The resin molded product according to any one of <7> to <9>, which is a portable electronic device part.
<11> The resin molded product according to any one of <8> to <10>, wherein the plated layer has performance as an antenna.
<12> After applying the laser to the surface of the resin molded product obtained by molding the thermoplastic resin composition for laser direct structuring according to any one of <1> to <6>, plating is performed. The manufacturing method of the resin molded product with a plating layer including forming a layer.
<13> The method for producing a resin molded article with a plating layer according to <12>, wherein the plating layer is a copper plating layer.
<14> A method for manufacturing a portable electronic device part having an antenna, including the method for manufacturing a resin-molded article with a plated layer according to <12> or <13>.

  It has become possible to provide a thermoplastic resin composition excellent in thermal conductivity, capable of forming an appropriate plating, and having excellent mechanical strength and fluidity. Furthermore, a resin molded product using the thermoplastic resin composition and a method for producing the resin molded product can be provided.

It is the schematic which shows the process of providing plating on the surface of a resin molded product. In FIG. 1, 1 indicates a resin molded product, 2 indicates a laser, 3 indicates a portion irradiated with the laser, 4 indicates a plating solution, and 5 indicates a plating layer.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

The thermoplastic resin composition for laser direct structuring of the present invention comprises a laser direct structuring additive 5 to 100 parts by weight of a resin component containing 60 to 100% by weight of a polycarbonate resin and 40 to 0% by weight of a styrene resin. 20 parts by weight, boron nitride 30-60 parts by weight, glass fiber 10-50 parts by weight, the laser direct structuring additive contains antimony and tin, the weight of the laser direct structuring additive and boron nitride The ratio (boron nitride / laser direct structuring additive) is 2-7.
Hereinafter, the configuration of the present invention will be described in detail.

<Resin component>
The resin composition of the present invention contains a resin component.
In the resin composition of the present invention, the resin component includes polycarbonate resin 60 to 100% by weight, styrene resin 40 to 0% by weight, polycarbonate resin 70 to 100% by weight, and styrene resin 30 to 0% by weight. It is more preferable.
The resin component may contain other resin components. However, the other resin is preferably 5% by weight or less of the total resin components. Only one type of resin component may be used, or two or more types may be used in combination.

<Polycarbonate resin>
The polycarbonate resin used in the present invention is not particularly limited, and any of an aromatic polycarbonate, an aliphatic polycarbonate, and an aromatic-aliphatic polycarbonate can be used. Of these, an aromatic polycarbonate is preferable, and a thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid is more preferable.

  As aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -P-diisopropylbenzene, hydroquinone, resorcinol, 4,4 -Dihydroxydiphenyl etc. are mentioned, Preferably bisphenol A is mentioned. Furthermore, for the purpose of preparing a composition having a high flame retardancy, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound, or a polymer containing both terminal phenolic OH groups having a siloxane structure or Oligomers and the like can be used.

  Preferred examples of the polycarbonate resin used in the present invention include polycarbonate resins derived from 2,2-bis (4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy compounds A polycarbonate copolymer derived from

  The molecular weight of the polycarbonate resin is preferably 14,000 to 30,000 in terms of viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, and 15,000 to 28,000. More preferably, it is 16,000 to 28,000. It is preferable for the viscosity average molecular weight to be in the above range since the mechanical strength becomes better and the moldability becomes better.

  The method for producing the polycarbonate resin is not particularly limited, and the present invention also uses a polycarbonate resin produced by any method such as the phosgene method (interfacial polymerization method) and the melting method (transesterification method). can do. Moreover, in this invention, after passing through the manufacturing process of a general melting method, you may use the polycarbonate resin manufactured through the process of adjusting the amount of OH groups of a terminal group.

  Furthermore, the polycarbonate resin used in the present invention may be not only a polycarbonate resin as a virgin raw material but also a polycarbonate resin regenerated from a used product, a so-called material-recycled polycarbonate resin.

  In addition, about the polycarbonate resin used by this invention, description of paragraph number 0018-0066 of Unexamined-Japanese-Patent No. 2012-072338 can be referred, for example, The content is integrated in this-application specification.

  The resin composition of the present invention may contain only one type of polycarbonate resin, or may contain two or more types.

<Styrene resin>
The resin composition of the present invention may contain a styrene resin as a resin component in addition to the polycarbonate resin. By blending a styrene resin, the fluidity tends to be further improved.

  Styrenic resin is a styrene polymer composed of styrene monomers, a copolymer of styrene monomers and other copolymerizable vinyl monomers, or styrene in the presence of a rubbery polymer. It means at least one polymer selected from the group consisting of a copolymer obtained by polymerizing a monomer or a styrene monomer and another copolymerizable vinyl monomer. Among these, it is preferable to use a styrene monomer or a copolymer of a styrene monomer and another copolymerizable vinyl monomer in the presence of a rubbery polymer.

  Specific examples of the styrene monomer include styrene derivatives such as styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, ethylvinylbenzene, dimethylstyrene, pt-butylstyrene, bromostyrene, and dibromostyrene. Among them, styrene is preferable. In addition, these can also be used individually or in mixture of 2 or more types.

  As vinyl monomers copolymerizable with the above styrenic monomers, vinylcyan compounds such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, Acrylic acid alkyl esters such as 2-ethylhexyl acrylate, octyl acrylate and cyclohexyl acrylate, methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate and cyclohexyl methacrylate Acrylic such as alkyl ester, phenyl acrylate, benzyl acrylate Aryl esters, aryl methacrylates such as phenyl methacrylate and benzyl methacrylate, epoxy group-containing acrylic or methacrylic esters such as glycidyl acrylate and glycidyl methacrylate, maleimides such as maleimide, N, N-methylmaleimide and N-phenylmaleimide Examples thereof include α, β-unsaturated carboxylic acids such as monomers, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid and itaconic acid, or anhydrides thereof.

  Further, rubbery polymers copolymerizable with styrene monomers include polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, acrylonitrile-butadiene random copolymers and block copolymers, acrylonitrile. -Butadiene copolymer, copolymer of alkyl acrylate or alkyl methacrylate and butadiene, polybutadiene-polyisoprene diene copolymer, ethylene-isoprene random copolymer and block copolymer, ethylene-butene random Copolymers of ethylene and α-olefins such as copolymers and block copolymers, ethylene-methacrylate copolymers, ethylene-butyl acrylate copolymers and the like of ethylene and α, β-unsaturated carboxylic acid esters Copolymer, D Examples include ethylene-propylene-nonconjugated diene terpolymers such as len-vinyl acetate copolymer, ethylene-propylene-hexadiene copolymer, acrylic rubber, and composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate or methacrylate rubber. Can be mentioned.

  Such styrene resins include, for example, styrene resin, high impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-acrylonitrile-butadiene. -Styrene copolymer (MABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin), styrene-methyl methacrylate copolymer (MS resin) ), Styrene-maleic anhydride copolymer, and the like.

  Among these, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene A copolymer (AES resin) is preferred, more preferably an acrylonitrile-butadiene-styrene copolymer (ABS resin), an acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), an acrylonitrile-ethylenepropylene rubber-styrene copolymer It is a coalescence (AES resin). Particularly preferred are acrylonitrile-butadiene-styrene copolymer (ABS resin) and acrylonitrile-styrene copolymer (AS resin).

  The styrene resin is produced by a method such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization, or bulk / suspension polymerization. In the present invention, the styrene resin or styrene random copolymer is used. In the case of a styrene block copolymer, those produced by bulk polymerization, suspension polymerization or bulk / suspension polymerization are suitable, and in the case of a styrene graft copolymer, bulk polymerization, bulk / suspension polymerization are used. Or what was manufactured by emulsion polymerization is suitable.

  In the present invention, an acrylonitrile-butadiene-styrene copolymer (ABS resin) that is particularly preferably used is a thermoplastic graft copolymer obtained by graft polymerization of acrylonitrile and styrene to a butadiene rubber component, and a copolymer of acrylonitrile and styrene. It is a mixture. The butadiene rubber component is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, and particularly preferably 13 to 25% by weight, in 100% by weight of the ABS resin component. The rubber particle diameter is preferably 0.1 to 5 μm, more preferably 0.2 to 3 μm, further 0.3 to 1.5 μm, and particularly preferably 0.4 to 0.9 μm. The rubber particle size distribution may be either a single distribution or a plurality of distributions of two or more peaks.

  In the present invention, an acrylonitrile-styrene copolymer (AS resin) particularly preferably used is a copolymer obtained by polymerizing acrylonitrile and styrene and may contain other components. Of the monomers constituting the AS resin, acrylonitrile preferably occupies 10 to 50 mol%, and more preferably 15 to 40 mol%. Moreover, it is preferable that styrene occupies 50-90 mol% among the monomers which comprise AS resin, and it is more preferable that 60-85 mol% is occupied.

  The resin composition of the present invention may contain only one type of styrenic resin, or may contain two or more types.

  In the resin composition of the present invention, 40% by weight or more of the total composition is preferably a resin component, more preferably 50% by weight or more is a resin component, and 60% by weight or more is a resin component. Is more preferable.

<Boron nitride>
The resin composition of the present invention contains boron nitride. By blending boron nitride, the thermal conductivity of the resin composition of the present invention can be greatly improved.

  The shape of boron nitride used in the present invention is not particularly limited, and any conventionally known shape can be used. Specific examples include a spherical shape, a linear shape (fiber shape), a flat plate shape (scale shape), a curved plate shape, and a needle shape. Then, it may be used as a single particle or as a granule (single particle aggregate). In the present invention, it is preferable to use a scale-like material because a resin composition excellent in thermal conductivity can be obtained and the mechanical properties become good.

  Boron nitride has several stable structures such as c-BN (zinc blende structure), w-BN (wurtzite structure), h-BN (hexagonal crystal structure), and r-BN (rhombohedral crystal structure). It has been. In the present invention, any boron nitride may be used. Among them, the use of hexagonal structure boron nitride provides sufficient thermal conductivity and wear of a molding machine or a mold used for obtaining a resin molded body. Is preferable. In addition, boron nitride includes a spherical shape and a scaly shape, and both can be used in the present invention. However, when a scaly shape is used, a molded product having more excellent thermal conductivity can be obtained. At the same time, the mechanical properties are favorable, which is preferable.

Although there is no restriction | limiting in the average particle diameter of the boron nitride used by this invention, Preferably it is 1-300 micrometers, More preferably, it is 2-200 micrometers, Furthermore, it is preferable that it is 5-100 micrometers.
As boron nitride, the thermal conductivity at 25 ° C. is preferably 30 W / (m · K) or more, and more preferably 50 W / (m · K) or more.

  The content of boron nitride in the resin composition of the present invention is 30 to 60 parts by weight, preferably 30 to 55 parts by weight, and preferably 30 to 50 parts by weight with respect to 100 parts by weight of the resin component. Is more preferable. When the boron nitride content is 30 parts by weight or more, the thermal conductivity is further improved, and when it is 60 parts by weight or less, the fluidity and moldability can be further improved.

<Laser direct structuring additive (LDS additive)>
The LDS additive used in the present invention is characterized by containing antimony and tin. Preferably, the component with the largest blending amount among the metal components blended with the LDS additive is tin, and the component with the next largest blending amount is antimony. Further, it preferably contains lead and / or copper. One of lead and copper may be included, or both may be included. In a preferred embodiment, tin is the component with the largest amount, antimony is the next component with the largest amount, lead is the metal component with the next largest amount, and metal with the next largest amount of lead. The aspect whose component is copper is illustrated.
The LDS additive in the present invention is obtained by adding 4 parts by weight of an additive considered to be an LDS additive to 100 parts by weight of polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, Iupilon (registered trademark), S-3000F). Using a 1064 nm YAG laser, irradiation was performed at an output of 10 W, a frequency of 80 kHz, and a speed of 3 m / s. The subsequent plating process was performed in an electroless MacDermid M-Copper85 plating tank, and metal was applied to the laser irradiation surface A compound that, when applied, can form a plating. The LDS additive used in the present invention may be a synthetic product or a commercial product. Moreover, as long as the commercially available product satisfies the requirements for the LDS additive in the present invention, it may be a material sold for other uses as well as those marketed as LDS additives.

The metal component contained in the LDS additive used in the present invention is 90% by weight or more of tin, 5% by weight or more of antimony, and preferably contains lead and / or copper as a minor component, and 90% by weight. The above is tin, 5-9% by weight is antimony, contains lead in the range of 0.01-0.1% by weight, and contains copper in the range of 0.001-0.01% by weight. Preferred (however, the total of the metal components does not exceed 100% by weight, the same applies hereinafter).
More specifically, the LDS additive used in the present invention preferably contains 90% by weight or more of tin oxide and 3 to 8% by weight of antimony oxide, and 0.01 to 0.1% by weight of lead oxide and It is preferable to contain 0.001 to 0.01% by weight of copper oxide. As a particularly preferred embodiment, LDS containing 90% by weight or more of tin oxide, 3 to 8% by weight of antimony oxide, 0.01 to 0.1% by weight of lead oxide, and 0.001 to 0.01% by weight of copper oxide. It is a form using an additive, and in a more preferred embodiment, tin oxide is 93 wt% or more, antimony oxide is 4 to 7 wt%, lead oxide is 0.01 to 0.05 wt%, and copper oxide is 0.1% by weight. In this embodiment, an LDS additive containing 001 to 0.006% by weight is used.

  The LDS additive used in the present invention may contain a trace amount of other metals in addition to lead and / or copper. Examples of other metals include indium, iron, cobalt, nickel, zinc, cadmium, silver, bismuth, arsenic, manganese, chromium, magnesium, calcium, and the like. These metals may exist as oxides. The content of these metals is preferably 0.001% by weight or less of the metal component contained in the LDS additive.

  The particle diameter of the LDS additive is preferably 0.01 to 50 μm, and more preferably 0.05 to 30 μm. By adopting such a configuration, the uniformity of the plating surface state tends to be good when plating is applied.

The compounding quantity of the LDS additive in the resin composition of this invention is 5-20 weight part with respect to 100 weight part of resin components, 5-15 weight part is preferable and 6-12 weight part is further more preferable.
The resin composition of the present invention may contain only one type of LDS additive, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
In the present invention, the weight ratio of LDS additive to boron nitride (boron nitride / LDS additive) is 2 to 7, preferably 3 to 6, and more preferably 4.5 to 5.5. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively.

<Glass fiber>
The resin composition of the present invention may contain glass fibers. Examples of the glass fiber include glass fiber, plate-like glass, glass beads, and glass flakes. Among these, glass fiber is preferable.

A glass fiber consists of glass compositions, such as A glass, C glass, E glass, and S glass, and since E glass (an alkali free glass) does not have a bad influence on polycarbonate resin especially, it is preferable.
Glass fiber refers to a fiber having a fiber-like outer shape with a cross-sectional shape cut at right angles to the length direction and having a perfect circle or polygonal shape.

The glass fiber used for the resin composition of the present invention may be a single fiber or a single fiber twisted together.
As for the form of the glass fiber, “glass roving” continuously wound up of single fibers or twisted ones, “chopped strand” trimmed to a length of 1 to 10 mm, and pulverized to a length of about 10 to 500 μm. Any of "Mildo fiber" etc. may be sufficient. Such glass fibers are commercially available from Asahi Fiber Glass Co., Ltd. under the trade names “Glasslon Chopped Strand” and “Glasslon Milled Fiber”, and are easily available. Glass fibers having different forms can be used in combination.

  In the present invention, glass fibers having an irregular cross-sectional shape are also preferable. This irregular cross-sectional shape means that the flatness indicated by the long diameter / short diameter ratio (D2 / D1) when the long diameter of the cross section perpendicular to the length direction of the fiber is D2 and the short diameter is D1, is, for example, 1. 5 to 10, particularly 2.5 to 10, more preferably 2.5 to 8, and particularly preferably 2.5 to 5. Regarding such flat glass, the description of paragraph numbers 0065 to 0072 of JP2011-195820A can be referred to, and the contents thereof are incorporated in the present specification.

  The glass beads are spherical ones having an outer diameter of 10 to 100 μm, and are commercially available, for example, from Potters Barotini under the trade name “EGB731” and are easily available. Further, the glass flake is a flake shape having a thickness of 1 to 20 μm and a length of one side of 0.05 to 1 mm, and is commercially available, for example, under the trade name “Fureka” from Nippon Sheet Glass Co., Ltd. Are readily available.

  In order to further improve the plating property of the resin composition of the present invention, a form using glass fibers having an average fiber length of 300 μm or less is exemplified. The glass fiber used in this form has an average fiber length of preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 120 μm or less, from the viewpoint of improving plating properties. Moreover, as a lower limit, 5 micrometers or more are preferable, More preferably, it is 7 micrometers or more, More preferably, it is 15 micrometers or more. Further, the average fiber diameter of the glass fiber is preferably 20 μm or less, more preferably 5 to 15 μm, further preferably 7 to 15 μm, and particularly preferably 9 to 15 μm. If the average fiber diameter is less than 5 μm, the moldability of the resin composition may be impaired. If the average fiber diameter exceeds 20 μm, the appearance of the resin molded product may be impaired, and the reinforcing effect may not be sufficient. is there. In the present invention, the average fiber length represents the weight average fiber length.

  When blended, the blending amount of the glass fiber in the resin composition of the present invention is 10 to 50 parts by weight, preferably 10 to 40 parts by weight, and more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the resin component. 12 to 28 parts by weight is particularly preferable. The resin composition of the present invention may contain only one type of glass fiber, or may contain two or more types. When two or more types are included, the total amount falls within the above range. By blending glass fiber, mechanical strength can be improved and plating properties tend to be improved.

<Elastomer>
The resin composition of the present invention preferably contains an elastomer. By containing the elastomer, the impact resistance of the resin composition can be improved.

  The elastomer used in the present invention is preferably a graft copolymer obtained by graft copolymerizing a rubbery polymer with a monomer component copolymerizable therewith. The method for producing the graft copolymer may be any method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft. From the viewpoint of easy control of productivity and particle size, an emulsion polymerization method is preferred, and a multistage emulsion polymerization method is more preferred. Examples of the multistage emulsion polymerization method include polymerization methods described in JP-A No. 2003-261629.

The rubbery polymer generally has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, (partial) hydrogenated polybutadiene rubber, butadiene-styrene copolymer, (partial) hydrogenated polybutadiene-styrene copolymer, butadiene-styrene block copolymer, (partial) water. One or more vinyl monomers that can be copolymerized with butadiene and butadiene, such as a polybutadiene-styrene block copolymer, a butadiene-acrylonitrile copolymer, and an acrylic rubber copolymer based on butadiene-isobutyl acrylate Butadiene rubber such as a copolymer with polyisobutylene, polyisobutylene, polyisobutylene-styrene copolymer, isobutylene rubber such as polyisobutylene-styrene block copolymer, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl) Acrylate), butyla Polyalkyl acrylate rubber such as relate / 2-ethylhexyl acrylate copolymer, silicone rubber such as polyorganosiloxane rubber, butadiene-acrylic composite rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, ethylene -Ethylene-alpha olefin rubbers such as propylene rubber, ethylene-butene rubber, ethylene-octene rubber, ethylene-acrylic rubber, fluorine rubber, and the like. These may be used alone or in admixture of two or more.
Among these, in view of mechanical properties and surface appearance, polybutadiene rubber, butadiene-styrene copolymer, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber. Is preferred. Here, IPN refers to an interpenetrating polymer network.

Specific examples of monomer components that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, and the like. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (For example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more.
Among these, aromatic vinyl compounds, vinyl cyanide compounds, and (meth) acrylic acid ester compounds are preferable, and (meth) acrylic acid ester compounds are more preferable from the viewpoint of mechanical properties and surface appearance. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to.

  The graft copolymer obtained by copolymerizing the rubber component is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Here, the core / shell type graft copolymer means one obtained by graft polymerization of a shell component around a rubber component, and does not necessarily require that the core and shell can be clearly distinguished. Among them, at least one rubber component selected from a polybutadiene-containing rubber, a polybutylacrylate-containing rubber, a polyorganosiloxane rubber, and an IPN type composite rubber composed of a polyorganosiloxane rubber and a polyalkylacrylate rubber is used as a core layer and a core layer. A core / shell type graft copolymer having a shell layer formed by copolymerizing (meth) acrylic acid ester is particularly preferable. The core / shell type graft copolymer preferably contains 40% by weight or more of rubber component, more preferably 60% by weight or more. Moreover, what contains 10 weight% or more of (meth) acrylic acid is preferable.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone IPN rubber) copolymers. Such rubbery polymers may be used alone or in combination of two or more.

  Examples of such a core / shell type graft copolymer include “Paraloid (registered trademark, hereinafter the same) EXL2602”, “Paraloid EXL2603”, “Paraloid EXL2655”, “Paraloid” manufactured by Rohm and Haas Japan. “EXL2311”, “Paraloid EXL2313”, “Paraloid EXL2315”, “Paraloid KM330”, “Paraloid KM336P”, “Paraloid KCZ201”, “Metabrene (registered trademark, the same applies hereinafter) C-223A”, “Metabrene E” manufactured by Mitsubishi Rayon Co., Ltd. -901 "," Metabrene S-2001 "," Metabrene SRK-200 "," Kane Ace (registered trademark, the same applies hereinafter) M-511 "," Kane Ace M-711 "," Kane Ace M-731 ", manufactured by Kaneka Corporation Kane Ace M-600 " "Kane Ace M-400", "Kane Ace M-580", and "Kane Ace MR-01", and the like.

  The lower limit when blending the elastomer content in the present invention is preferably 0.5 parts by weight or more, more preferably 2 parts by weight or more, further preferably 3 parts by weight or more with respect to 100 parts by weight of the resin component. It is. The upper limit is preferably 10 parts by weight or less, more preferably 8 parts by weight or less.

  The resin composition of the present invention may contain only one type of elastomer or two or more types. When two or more types are included, the total amount falls within the above range.

<Phosphorus stabilizer>
The resin composition of the present invention preferably contains a phosphorus stabilizer, and more preferably contains an organic phosphorus stabilizer. By blending the organophosphorus stabilizer, the polycarbonate resin by the LDS additive is hardly decomposed, and the effect of the present invention is more effectively exhibited. As the organophosphorous stabilizer, the description of paragraphs 0073 to 0095 of JP-A-2009-35691 can be referred to, and the contents thereof are incorporated in the present specification. A more preferable organophosphorus stabilizer is a compound represented by the following general formula (3).

General formula (3)
O = P (OH) _m (OR) _3-m (3)
(In general formula (3), R is an alkyl group or an aryl group, and may be the same or different. M is an integer of 0-2.)
R is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and an alkyl group having 2 to 25 carbon atoms, a phenyl group, a nonylphenyl group, a stearylphenyl group, 2,4- A di-tert-butylphenyl group, a 2,4-ditert-butylmethylphenyl group, and a tolyl group are more preferable.

  Among these, phosphates represented by the following general formula (3 ') are preferable.

O = P (OH) _{m ′} (OR ′) _{3-m ′} (3 ′)
In general formula (3 ′), R ′ is an alkyl group having 2 to 25 carbon atoms, which may be the same or different. m ′ is 1 or 2. Here, examples of the alkyl group include octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, hexadecyl group, octadecyl group and the like. A tetradecyl group, a hexadecyl group and an octadecyl group are preferable, and an octadecyl group is particularly preferable.

  Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, tetrakis (2,4-di-). tert-butylphenyl) -4,4-diphenylene phosphonite, monostearyl acid phosphate, distearyl acid phosphate, and the like.

（一般式（４）中、Ｒ'は、アルキル基またはアリール基であり、各々同一でも異なっていてもよい。）
Ｒ'は炭素数１〜２５のアルキル基または、炭素数６〜１２のアリール基であることが好ましい。Ｒ’がアルキル基である場合、炭素数１〜３０のアルキル基が好ましい。Ｒ’がアリール基である場合、炭素数６〜３０のアリール基が好ましい。 As the phosphite, a compound represented by the following general formula (4) is also preferable.
General formula (4)

(In general formula (4), R ′ is an alkyl group or an aryl group, and each may be the same or different.)
R ′ is preferably an alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 12 carbon atoms. When R ′ is an alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable. When R ′ is an aryl group, an aryl group having 6 to 30 carbon atoms is preferable.

  Examples of phosphites include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, trinonyl phosphite, tridecyl phosphite, and trioctyl phosphite. , Trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, monobutyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol phosphite Phosphorous such as bis (2.6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite Triesters of, diesters, monoesters, and the like.

  When the resin composition of the present invention contains a phosphorus stabilizer, the amount of the phosphorus stabilizer is preferably 0.01 to 5 parts by weight and more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the resin component. Preferably, 0.08 to 0.5 part by weight is more preferable. By making it 0.01 parts by weight or more, decomposition of the polycarbonate resin by the LDS additive can be more effectively suppressed, and by making it 5 parts by weight or less, the adhesion strength between the glass fiber and the polycarbonate is increased, The strength can be further improved.

  The resin composition of the present invention may contain only one type of phosphorus stabilizer, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Antioxidant>
The resin composition of the present invention may contain an antioxidant. As the antioxidant, a phenolic antioxidant is preferable, and more specifically, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3,5-di-t-). Butyl-4'-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4- Hydroxybenzyl) isocyanurate, 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-hydroxy-5-methylphenyl) propionate], And 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethyl Ruechiru} -2,4,8,10-spiro [5,5] undecane. Among them, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is preferable.

When the resin composition of this invention contains antioxidant, it is preferable that the compounding quantity of antioxidant is 0.01-5 weight part with respect to 100 weight part of resin components, 0.05-3 weight part Is more preferable.
The resin composition of the present invention may contain only one kind of antioxidant or two or more kinds. When two or more types are included, the total amount is preferably within the above range.

<Release agent>
The resin composition of the present invention may contain a release agent. The release agent is preferably at least one compound selected from aliphatic carboxylic acids, aliphatic carboxylic acid esters, and aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000. Among these, at least one compound selected from aliphatic carboxylic acids and aliphatic carboxylic acid esters is more preferably used.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. In the present specification, the term “aliphatic carboxylic acid” is used to include alicyclic carboxylic acids. Among the aliphatic carboxylic acids, mono- or dicarboxylic acids having 6 to 36 carbon atoms are preferable, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellic acid, and tetrariacontanoic acid. , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.

  As the aliphatic carboxylic acid component constituting the aliphatic carboxylic acid ester, the same aliphatic carboxylic acid as that described above can be used. On the other hand, examples of the alcohol component constituting the aliphatic carboxylic acid ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Of these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic alcohol also includes an alicyclic alcohol. Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc. These aliphatic carboxylic acid esters may contain an aliphatic carboxylic acid and / or alcohol as impurities, and may be a mixture of a plurality of compounds. Specific examples of the aliphatic carboxylic acid ester include beeswax (mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, octyldodecyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin Examples thereof include distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

When the resin composition of this invention contains a mold release agent, it is preferable that the compounding quantity of a mold release agent is 0.01-8 weight part with respect to 100 weight part of resin components, 0.1-6 weight part Is more preferable.
The resin composition of the present invention may contain only one type of release agent, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Titanium oxide>
The resin composition of the present invention preferably contains titanium oxide.
As titanium oxide, it is preferable to use titanium oxide containing 80% by weight or more of titanium oxide from the viewpoint of whiteness and hiding properties among those commercially available. Examples of the titanium oxide used in the present invention include titanium monoxide (TiO), titanium trioxide (Ti ₂ O ₃ ), titanium dioxide (TiO ₂ ), and any of these may be used. Titanium dioxide is preferred. Further, as the titanium oxide, those having a rutile type crystal structure are preferably used.
When the resin composition of this invention contains a titanium oxide, it is preferable that the compounding quantity of a titanium oxide contains 0.5-10 weight part with respect to 100 weight part of resin components, and contains 1.0-6 weight part. It is more preferable. The resin composition of the present invention may contain only one type of titanium oxide or two or more types. When two or more types are included, the total amount falls within the above range.

The resin composition of the present invention may contain other components without departing from the spirit of the present invention. Other components include stabilizers other than phosphorus stabilizers, flame retardants, UV absorbers, fluorescent brighteners, antistatic agents, antifogging agents, lubricants, antiblocking agents, fluidity improvers, plasticizers, dispersions Agents, antibacterial agents and the like. Two or more of these may be used in combination.
About these components, description of Unexamined-Japanese-Patent No. 2007-314766, Unexamined-Japanese-Patent No. 2008-127485, Unexamined-Japanese-Patent No. 2009-51989, Unexamined-Japanese-Patent No. 2012-72338, etc. can be referred, These content is this specification. Embedded in the book.

  The method for producing the resin composition of the present invention is not particularly defined, and a wide variety of known methods for producing a thermoplastic resin composition can be adopted. Specifically, each component is mixed in advance using various mixers such as a tumbler or Henschel mixer, and then melt kneaded with a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. By doing so, a resin composition can be produced.

Also, for example, without mixing each component in advance, or by mixing only a part of the components in advance, and supplying to an extruder using a feeder and melt-kneading to produce the resin composition of the present invention You can also.
Furthermore, for example, a resin composition obtained by mixing some components in advance, supplying them to an extruder and melt-kneading is used as a master batch, and this master batch is mixed with the remaining components again and melt-kneaded. The resin composition of the present invention can also be produced.

  The method for producing the resin molded product is not particularly limited, and a molding method generally adopted for the thermoplastic resin composition can be arbitrarily adopted. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, Examples thereof include a blow molding method. A molding method using a hot runner method can also be used.

Next, the process of providing plating on the surface of a resin molded product obtained by molding the resin composition of the present invention will be described with reference to FIG. FIG. 1 is a schematic view showing a process of forming plating on the surface of a resin molded product 1 by a laser direct structuring technique. In FIG. 1, the resin molded product 1 is a flat substrate. However, the resin molded product 1 is not necessarily a flat substrate, and may be a resin molded product having a partially or entirely curved surface. Further, the resin molded product is not limited to the final product, and includes various parts. As the resin molded product in the present invention, a portable electronic device component is preferable. Portable electronic device parts have both high impact resistance, rigidity, and excellent heat resistance, as well as low anisotropy and low warpage. PDAs such as electronic notebooks and portable computers, pagers, and mobile phones. It is extremely effective as an internal structure such as a telephone or a PHS and a housing. Especially, the resin molded product has an average thickness excluding ribs of 1.2 mm or less (the lower limit is not particularly defined, but, for example, 0.4 mm or more) ), Which is particularly suitable as a housing.
Moreover, it is suitable for the use as which evaluation of the UL-94 test of the resin molded product in an average thickness of 1.6 mm is V-0.

Returning again to FIG. 1, the resin molded product 1 is irradiated with a laser 2. The laser here is not particularly defined, and can be appropriately selected from known lasers such as a YAG laser, an excimer laser, and electromagnetic radiation, and a YAG laser is preferable. Further, the wavelength of the laser is not particularly defined. A preferable wavelength range is 200 nm to 1200 nm. Especially preferably, it is 800-1200 nm.
When the laser is irradiated, the resin molded product 1 is activated only in the portion 3 irradiated with the laser. In this activated state, the resin molded product 1 is applied to the plating solution 4. The plating solution 4 is not particularly defined, and a wide variety of known plating solutions can be used. The metal component preferably contains at least one of copper, nickel, gold, silver and palladium, and contains copper. Is more preferable.
The method of applying the resin molded product 1 to the plating solution 4 is not particularly defined, but for example, a method of introducing the resin molded product 1 into a solution containing the plating solution. In the resin molded product after applying the plating solution, the plating layer 5 is formed only in the portion irradiated with the laser.
In the method of the present invention, a circuit interval having a width of 1 mm or less and further 150 μm or less (the lower limit is not particularly defined, but for example, 30 μm or more) can be formed. In order to suppress corrosion and deterioration of the formed circuit, the plating can be further protected with nickel or gold after performing electroless plating, for example. Similarly, a necessary film thickness can be formed in a short time by using electroplating after electroless plating.

Molded articles obtained from the resin composition of the present invention include, for example, electronic parts such as connectors, switches, relays, conductive circuits, reflectors such as lamp reflectors, sliding parts such as gears and cams, air intake manifolds, etc. It can be used for various parts such as automobile parts, water-related parts such as sinks, various decorative parts, films, sheets, fibers and the like.
The resin composition of the present invention gives a molded article having high whiteness and excellent reflectance, depending on the molding method. The whiteness (Hunter type) of the molded product obtained from the resin composition of the present invention is usually 92 or more, preferably 94 or more. Moreover, the molded article obtained from the resin composition of the present invention is excellent in heat resistance and light stability in an actual use environment. Therefore, the molded product obtained from the resin composition of the present invention functions as a component having a function of reflecting light, particularly an LED device component, preferably an LED reflector or a conductive circuit. Only one layer may be sufficient as a plating layer, and a multilayered structure may be sufficient as it.

  In addition, within the range which does not deviate from the meaning of the present invention, JP2011-219620A, JP2011-195820A, JP2011-178873A, JP2011-168705A, JP2011-148267A. The description of the publication can be taken into consideration.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate 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.

<Resin>
PC resin: polycarbonate resin, Iupilon E-2000, manufactured by Mitsubishi Engineering Plastics, aromatic polycarbonate resin starting from bisphenol A, viscosity average molecular weight: 27000
ABS resin: Santac AT-08, Nippon A & L AS resin: Technopolymer 290FF, Technopolymer

<Boron nitride (BN)>
PW50: Boron nitride, manufactured by Zibo Jony Ceramic Technologies

<LDS additive>
CP5C: manufactured by Keeling & Walker, antimony-doped tin oxide (consisting of 95% by weight of tin oxide, 5% by weight of antimony oxide, 0.02% by weight of lead oxide, and 0.004% by weight of copper oxide)

<Antioxidant>
Irg1076: manufactured by BASF, Irganox1076
<Phosphorus stabilizer>
AX-71: ADEKA, mono- and di-stearyl acid phosphate almost equimolar mixture

<Release agent>
VPG861: Pentaerythritol tetrastearate, manufactured by Cognis Oleochemicals Japan

<Elastomer>
M711: Kane Ace, made by Kaneka

<Glass fiber>
T-187: manufactured by Nippon Electric Glass Co., Ltd., average fiber length of 3 mm, average fiber diameter of 13 μm, glass fiber having a circular cross section (flatness: 1)

<Titanium oxide>
CP-K: Titanium oxide manufactured by Resino Color Industry

<Compound>
Each component was weighed so as to have the composition shown in the table to be described later, mixed with a tumbler for 20 minutes, then supplied to Nippon Steel Works (TEX30HSST) equipped with 1 vent, screw rotation speed 200 rpm, discharge The molten resin, which was kneaded under the conditions of an amount of 20 kg / hour and a barrel temperature of 280 ° C. and extruded into a strand, was rapidly cooled in a water tank and pelletized using a pelletizer to obtain pellets of a resin composition.

<Evaluation of fluidity: Q value (unit: 0.01 cm ³ / sec)>
After the pellets obtained above were dried at 100 ° C. for 4 hours or more, using a high load type flow tester, the effluent Q value per unit time of the composition under the conditions of 278 ° C. and load 160 kgf (unit: 0) .01 cm ³ / sec) was measured to evaluate the fluidity. An orifice having a diameter of 1 mm and a length of 10 mm was used.

<Tensile test>
<< Tensile modulus, tensile fracture point strength, tensile fracture point nominal strain >>
After drying the resin composition pellet obtained by the above method at 100 ° C. for 5 hours, using an injection molding machine (“J55-60H” manufactured by Nippon Steel Co., Ltd.), a cylinder set temperature of 270 to 290 ° C., a mold temperature Injection molding was performed under the conditions of 100 ° C., injection time of 2 seconds, and molding cycle of 40 seconds, and an ISO multipurpose test piece (4 mm thick) was injection molded.
Using the obtained ISO test piece, the tensile elastic modulus (unit: MPa), tensile fracture point strength (unit: MPa), tensile fracture point at a temperature of 23 ° C. in accordance with ISO standard 527-1 and ISO527-2 The nominal strain (unit:%) was measured.

<Bending test>
Using a bending test piece (thickness 4 mm) manufactured in the same manner as the above tensile property evaluation, the bending elastic modulus (unit: MPa) and bending stress (unit: MPa) were measured at a temperature of 23 ° C. in accordance with ISO178. It was measured.

<Measurement of thermal conductivity (unit: W / m · K)>
The ISO multipurpose test piece obtained above was cut into a slice of 0.15 to 0.5 mm thickness, and this was used as a sample using a temperature wave thermal analyzer “ai-Phase Mobile1” manufactured by I-Phase Co., Ltd. The MD direction (resin flow direction during molding) and the thickness direction were measured.

<LDS activity-Placing Index>
Using a 1064 nm YAG laser on the surface of a 2 mm / 3 mm thick two-stage plate, laser irradiation was performed under conditions of an output of 10 W, a frequency of 80 kHz, and a speed of 3 m / s, followed by plating of MacDermid M-Copper85 Electroless plating was performed on the layers. From the thickness of the copper plating, the LDS activity was evaluated as follows. The thicker the thickness, the higher the plating property.

The results are shown in the table below.

  As is clear from the above table, the resin composition of the present invention has high fluidity and is excellent in tensile test, bending test, thermal conductivity and plating property.

Claims (14)

5 to 20 parts by weight of a laser direct structuring additive and 30 to 60 parts by weight of boron nitride with respect to 100 parts by weight of a resin component containing 60 to 83.5 % by weight of polycarbonate resin and 40 to 16.5 % by weight of styrene resin And the laser direct structuring additive contains antimony and tin, and the weight ratio of the laser direct structuring additive to boron nitride (boron nitride / laser direct structuring additive) ) is 3-6, the laser direct structuring thermoplastic resin composition. The thermoplastic resin composition for laser direct structuring according to claim 1, wherein the styrenic resin is an acrylonitrile-butadiene-styrene copolymer. Furthermore, the thermoplastic resin composition for laser direct structuring of Claim 1 or 2 containing the elastomer which is a core / shell type graft copolymer . A core layer in which the elastomer includes at least one rubber component selected from polybutadiene-containing rubber, polybutylacrylate-containing rubber, polyorganosiloxane rubber, and IPN type composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber The thermoplastic resin for laser direct structuring according to claim 3, wherein the core layer is a core / shell graft copolymer having a shell layer formed by copolymerizing a (meth) acrylic acid ester on the core layer. Resin composition. The thermoplastic resin composition for laser direct structuring according to any one of claims 1 to 4, wherein the component having the largest blending amount among the metal components contained in the laser direct structuring additive is tin. The thermoplastic resin composition for laser direct structuring according to any one of claims 1 to 5, further comprising a phosphorus-based stabilizer and / or an antioxidant. The resin molded product formed by shape | molding the thermoplastic resin composition for laser direct structuring of any one of Claims 1-6. Furthermore, the resin molded product of Claim 7 which has a plating layer on the surface. The resin molded product according to claim 8 , wherein the plated layer retains performance as an antenna. The resin molded product according to any one of claims 7 to 9 , which is a mechanical component. The resin molded product according to any one of claims 7 to 9 , which is a portable electronic device part. A metal layer is applied to the surface of a resin molded product formed by molding the thermoplastic resin composition for laser direct structuring according to any one of claims 1 to 6, and a plating layer is formed by applying a metal. The manufacturing method of the resin molded product with a plating layer including doing. The manufacturing method of the resin molded product with a plating layer of Claim 12 whose said plating layer is a copper plating layer. A method for manufacturing a portable electronic device part having an antenna, comprising the method for manufacturing a resin molded product with a plated layer according to claim 12 or 13.

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