JP5599929B1 - Resin composition, resin molded product, and method for producing resin molded product - Google Patents

Abstract

[PROBLEMS] To provide a resin composition for laser direct structuring excellent in various mechanical properties such as bending elastic modulus, bending strength, Charpy impact strength and deflection temperature under load and flame retardancy while maintaining plating properties.
5 to 40 parts by weight of glass fibers having an average fiber length / average fiber diameter of 10 or less with respect to 100 parts by weight of a resin component containing 65 to 90% by weight of a polycarbonate resin and 35 to 10% by weight of a styrene resin. Resin composition containing 0.5 to 10 parts by weight of elastomer, 5 to 10 parts by weight of laser direct structuring additive containing antimony and tin, 10 to 30 parts by weight of phosphazene compound and 0.1 to 1 part by weight of polytetrafluoroethylene .
[Selection figure] None

Description

  The present invention relates to a 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 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, also in the said resin composition for LDS, the request | requirement of high flame retardance is high. On the other hand, mechanical strength is also required for the resin composition for LDS. Naturally, plating properties are also required. Further, the LDS additive is necessary for forming the plating, but can be a foreign matter in the resin molded product. The object of the present invention is to provide a resin composition for LDS that is excellent in flame retardancy while maintaining mechanical strength and plating properties.

Under such circumstances, as a result of intensive studies by the present inventor, the above problem has been solved by the following means <1>, preferably <2> to <16>.
<1> 5 to 40 parts by weight of glass fiber having an average fiber length / average fiber diameter of 10 or less, and an elastomer with respect to 100 parts by weight of a resin component containing 65 to 90% by weight of polycarbonate resin and 35 to 10% by weight of styrene resin Laser direct structuring containing 0.5 to 10 parts by weight, laser direct structuring additive containing 5 to 10 parts by weight of antimony and tin, 10 to 30 parts by weight of phosphazene compound and 0.1 to 1 part by weight of polytetrafluoroethylene Resin composition.
<2> The resin composition according to <1>, wherein an amount of the glass fiber having an average fiber length / average fiber diameter of 10 or less is 5 to 30 parts by weight with respect to 100 parts by weight of the resin component.
<3> The resin composition according to <1> or <2>, further containing 0.5 to 5 parts by weight of titanium oxide with respect to 100 parts by weight of the resin component.
<4> The resin composition according to any one of <1> to <3>, wherein the component having the largest blending amount among the metal components contained in the laser direct structuring additive is tin.
<5> The resin composition according to any one of <1> to <4>, wherein the laser direct structuring additive includes 90% by weight or more of tin oxide and 3 to 8% by weight of antimony oxide.
<6> The laser direct structuring additive includes any of <1> to <5>, wherein the lead oxide includes 0.01 to 0.1% by weight of lead oxide and / or 0.001 to 0.01% by weight of copper oxide. The resin composition as described.
<7> The resin composition according to any one of <1> to <6>, wherein the elastomer is a siloxane copolymer elastomer.
<8> Glass fibers having an average fiber length / average fiber diameter of more than 10 are included at a ratio of 100% by weight or less of the blend amount of glass fibers having an average fiber length / average fiber diameter of 10 or less. 7> The resin composition in any one of.
<9> A resin molded product obtained by molding the resin composition according to any one of <1> to <8>.
<10> The resin molded product according to <9>, wherein the evaluation of the UL-94 test of the resin molded product at a thickness of 1.6 mm is V-0.
<11> The resin molded product according to <9> or <10>, which has a plating layer on the surface of the resin molded product.
<12> The resin molded product according to any one of <9> to <11>, which is a portable electronic device component.
<13> The resin molded product according to <11> or <12>, wherein the plated layer has performance as an antenna.
<14> including applying a metal to the surface of a resin molded product formed by molding the resin composition according to any one of <1> to <8>, and then applying a metal to form a plating layer. The manufacturing method of the resin molded product with a plating layer.
<15> The method for producing a resin molded article with a plating layer according to <14>, wherein the plating layer is a copper plating layer.
<16> A method for manufacturing a portable electronic device component having an antenna, including the method for manufacturing a resin-molded article with a plated layer according to <14> or <15>.

  According to the present invention, it is possible to provide a resin composition excellent in flame retardancy while maintaining mechanical strength and plating properties.

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. In the present specification, “(meth) acrylate” represents acrylate and methacrylate, and “(meth) acryl” represents acryl and methacryl.

The resin composition for LDS of the present invention is a glass fiber having an average fiber length / average fiber diameter of 10 or less with respect to 100 parts by mass of a resin component containing 65 to 90% by weight of a polycarbonate resin and 35 to 10% by weight of a styrene resin. 5 to 40 parts by weight, 0.5 to 10 parts by weight of an elastomer, 5 to 10 parts by weight of a laser direct structuring additive containing antimony and tin, 10 to 30 parts by weight of a phosphazene compound, and 0.1 to 1 part by weight of polytetrafluoroethylene It is characterized by including a part. As described above, by using glass fibers having an average fiber length / average fiber diameter of 10 or less (hereinafter sometimes referred to as “short fibers”), while maintaining mechanical strength and plating properties, flame retardancy is achieved. An excellent resin composition can be provided. Glass fiber is well known as a component to be blended in order to improve mechanical strength, but it is very surprising that flame retardancy is improved by blending such glass fiber, particularly short fiber.
Hereinafter, details of the resin composition of the present invention will be described.

<Resin component>
The resin composition of the present invention contains a resin component.
In the resin composition of the present invention, the resin component contains 65 to 90% by weight of polycarbonate resin and 35 to 10% by weight of styrene resin, 68 to 90% by weight of polycarbonate resin and 32 to 10% by weight of styrene resin. 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.

  Examples of the aromatic dihydroxy compound include 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. It is more preferable that it is 16,000 to 26,000. 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.

<< Styrenic resin >>
The resin composition of the present invention contains a styrene resin in addition to the polycarbonate resin as a resin component.

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

  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 combination (AES resin), and an acrylonitrile-butadiene-styrene copolymer (ABS resin) is particularly preferable.

  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 polymer or block copolymer, those produced by bulk polymerization, suspension polymerization, or bulk / suspension polymerization are suitable. In the case of a styrene-based graft copolymer, bulk polymerization, bulk / suspension polymerization or Those produced by emulsion polymerization are preferred.

  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.

  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.

<Glass fiber (short fiber)>
The resin composition of the present invention includes glass fibers (short fibers) having an average fiber length / average fiber diameter of 10 or less. By using such short fibers, the flame retardancy of the resin composition of the present invention can be improved. Furthermore, it becomes possible to improve the anisotropy and the surface appearance more effectively. The aspect ratio of the short fiber is preferably 8 or less, more preferably 7 or less, and preferably 2.5 or more, more preferably 3 or more. When the aspect ratio exceeds 10, warpage and anisotropy increase, and the appearance of the molded product tends to deteriorate.
The short fiber used in the present invention is preferably a glass fiber milled fiber. Milled glass fiber is obtained by milling glass fiber chopped strands obtained by cutting glass fiber strands obtained by bundling tens to thousands of glass single fibers (filaments) into a predetermined length. In this case, the glass fiber chopped strand is preferably surface-treated with a sizing agent as described later.

  Moreover, it is preferable that the average fiber diameter of the short fiber used by this invention is 1-25 micrometers, More preferably, it is 5-17 micrometers. When the average fiber diameter is 1 μm or more, moldability tends to be improved, and when the average fiber diameter is 25 μm or less, the appearance becomes better and the reinforcing effect becomes more effective. The average fiber length is preferably 1 to 500 μm, more preferably 10 to 300 μm, and still more preferably 20 to 200 μm.

  The average fiber diameter of the short fibers used in the present invention refers to the number average fiber diameter, and the average fiber length refers to the number average fiber length in the pellet of the present invention.

  Moreover, as a short fiber used by this invention, both the thing of a circular cross-sectional shape and the thing of an irregular cross-sectional shape are preferable, and the thing of a circular cross-sectional shape is more preferable. When the one having a circular cross-sectional shape is used, the weld strength of the obtained molded product can be further improved.

  The short fibers used in the present invention include glass compositions such as A glass, C glass, and E glass. Among them, E glass (non-alkali glass) is preferable because it does not adversely affect the polycarbonate resin.

There is no particular limitation on the sizing agent when surface-treating the glass fiber chopped strand for producing the above-mentioned milled glass fiber, for example, urethane-based, epoxy-based, acrylic-based, polyester-based, styrene-based, olefin-based, etc. Sizing agents. Of these, urethane-based and epoxy-based sizing agents are more preferable, and epoxy-based sizing agents are more preferable.
In addition, the adhesion amount of a sizing agent is 0.1 to 3 weight% normally in 100 weight% of glass fibers, Preferably it is 0.2 to 1 weight%.

The compounding quantity of the short fiber in the resin composition of this invention is 5-40 weight part with respect to 100 weight part of resin components, 10-40 weight part is preferable, 12-40 weight part is more preferable, 15-40 Part by weight is more preferred. In particular, by setting the blending amount of the short fibers to 40 parts by weight or less with respect to 100 parts by weight of the resin component, in addition to flame retardancy, the plating property tends to be further improved.
The resin composition of the present invention may contain only one type of short fiber, or may contain two or more types. When two or more types are included, the total amount falls within the above range.

<Other glass fibers>
The resin composition of the present invention may contain glass fibers other than the short fibers. Glass fibers other than short fibers are glass fibers having an average fiber length / average fiber diameter of more than 10. By blending such other glass fibers, the bending elastic modulus and bending strength can be improved more effectively. The glass fiber having an average fiber length / average fiber diameter of more than 10 preferably has an average fiber length / average fiber diameter of 11 to 60.
50-450 micrometers is preferable and, as for the average fiber length of the other glass fiber used by this invention, 100-300 micrometers is more preferable. On the other hand, the average fiber diameter is preferably 3 to 18 μm, more preferably 5 to 14 μm. Examples of such other glass fibers include “glass roving”. 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.
Another glass fiber consists of glass compositions, such as A glass, C glass, and E glass, and E glass (an alkali free glass) is especially preferable.

  In the present invention, as the other glass fibers, those having a circular cross-sectional shape and irregular cross-sectional shapes are preferable, and those having a circular cross-sectional shape are more preferable. When the one having a circular cross-sectional shape is used, the weld strength of the obtained molded product can be further improved.

  Other glass fibers may be surface-treated with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. The adhesion amount is usually 0.01 to 1% by weight of the weight of the glass fiber. Furthermore, if necessary, a lubricant such as a fatty acid amide compound, silicone oil, an antistatic agent such as a quaternary ammonium salt, a resin having a film forming ability such as an epoxy resin or a urethane resin, a resin having a film forming ability and a heat. What was surface-treated with a mixture of a stabilizer, a flame retardant, etc. can also be used.

When blended, the blending amount of the other glass fibers in the resin composition of the present invention is preferably 100% by weight or less of the blending amount of the short fibers, and more preferably 10 to 50% by weight. By setting it as such a range, a bending elastic modulus and bending strength can be improved more effectively. On the other hand, for applications that do not require the effects of flexural modulus and flexural strength, for example, the other glass fiber can be 5% by mass or less.
The resin composition of the present invention may contain only one type of other glass fiber, or may contain two or more types. When two or more types are included, the total amount falls within the above range.
In the resin composition of the present invention, it is usually preferable that the resin component and glass fiber (total of short fibers and other glass fibers) account for 70% by weight or more of the total components.

<Elastomer>
The resin composition of the present invention contains an elastomer. By containing the elastomer, the impact resistance of the resin composition can be improved. The elastomer used in the present invention includes methyl methacrylate-butadiene-styrene copolymer (MBS resin), methyl methacrylate-butadiene rubber copolymer (MB resin), styrene-butadiene triblock called SBS, SEBS. Copolymer and its hydrogenated product, Styrene-isoprene triblock copolymer called SPS and SEPS and its hydrogenated product, Olefin thermoplastic elastomer called TPO, polyester elastomer, siloxane type Examples thereof include rubber, acrylate rubber, and siloxane copolymer elastomer. As the elastomer, the elastomer described in paragraphs 0075 to 0088 of JP2012-251061A, the elastomer described in paragraph numbers 0101 to 0107 of JP2012-1777047A, and the like can be used. It is incorporated herein. In the present invention, MBS resin, MB resin or siloxane copolymer elastomer is particularly preferably used, and a siloxane copolymer elastomer is more preferable.

(Siloxane copolymer elastomer)
The siloxane copolymer elastomer used in the present invention is preferably a silicone-acrylic composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate, and is composed of one or more vinyl compound monomers as required. A graft copolymer obtained by grafting a vinyl polymer may be used.

  The basic polymer structure includes an inner core layer comprising a structure in which polyorganosiloxane and polyalkyl (meth) acrylate, which are crosslinking components having a low glass transition temperature, are entangled with each other, and one or more vinyl compounds. A multilayer structure polymer having an outer shell layer made of a vinyl polymer composed of a monomer. The vinyl polymer constituting the outer shell layer has an effect of improving the adhesiveness with the matrix component of the resin composition. Such a graft copolymer can be produced, for example, by the method disclosed in Japanese Patent Application Laid-Open No. 2004-359889.

  The polyorganosiloxane used for the production of the silicone-acrylic composite rubber is not particularly limited, but for example, a polymer containing a dimethylsiloxane unit as a constituent unit is preferable. Examples of the dimethylsiloxane constituting the polyorganosiloxane include a dimethylsiloxane-based cyclic body having a 3-membered ring or more, and a 3- to 7-membered ring is preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These may be used alone or in admixture of two or more. Among these, the main component is preferably octamethylcyclotetrasiloxane from the viewpoint of easy control of the particle size distribution.

  The polyorganosiloxane may contain a siloxane containing a vinyl polymerizable functional group as a constituent component, or may be crosslinked with a siloxane-based crosslinking agent. Moreover, there is no restriction | limiting in particular also about the manufacturing method of a polyorganosiloxane, and the manufacturing method of a graft copolymer. These can be referred to the description in paragraphs [0055] to [0080] of JP 2012-131934 A, the contents of which are incorporated in the present specification.

  The number average particle diameter of the polyorganosiloxane is preferably 10 nm or more, more preferably 50 nm to 5 μm, and further preferably 100 nm to 3 μm. By setting the number average particle diameter of the polyorganosiloxane to 10 nm or more, the amount of polyalkyl (meth) acrylate in the silicone-acrylic composite rubber does not increase excessively, and the impact resistance can be prevented from being lowered.

The polyalkyl (meth) acrylate used for the production of the silicone-acrylic composite rubber is a polymer containing an alkyl (meth) acrylate unit.
Examples of the alkyl (meth) acrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and methyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n- Examples thereof include alkyl methacrylates such as lauryl methacrylate. These can be used alone or in combination of two or more.

  Further, the polyalkyl (meth) acrylate may be a copolymer containing a polyfunctional monomer unit as a constituent component. Examples of the polyfunctional monomer include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyania. Examples include nurate. These can be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in content in the case of using a polyfunctional monomer, It is preferable that it is 0.1 to 2 weight% in 100 weight% of polyalkyl (meth) acrylate, 0.3 to 1 More preferably, it is% by weight. By setting the content of the polyfunctional monomer to 0.1% by weight or more, there is a tendency to suppress a decrease in impact strength due to a change in the morphology of the composite rubber, and the content of the polyfunctional monomer. When the content is 2% by weight or less, the impact strength tends to be further improved.

  In the present invention, the siloxane copolymer elastomer may be a graft polymer obtained by graft polymerization of an alkyl methacrylate polymer to a polyorganosiloxane-polyalkyl (meth) acrylate composite rubber, or a polyorganosiloxane-polyalkyl (meth) acrylate. A graft copolymer obtained by graft-polymerizing acrylonitrile-styrene copolymer to a composite rubber is preferable, and these are marketed as “Metabrene S Series” by Mitsubishi Rayon Co., for example, “S-2030” or the like is used. It is preferable.

The compounding amount of the elastomer is 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, and more preferably 3 to 7 parts by weight with respect to 100 parts by weight of the resin component.
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.

<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-Copper 85 plating tank, and the laser irradiation surface was metal-coated. A compound that can form a plating when is applied. 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. preferable.
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 5-10 weight part with respect to 100 weight part of resin components, and 5-8 weight part is preferable. Further, by blending talc, sufficient plating properties can be achieved even if the blending amount of the LDS additive is small (for example, 3 to 7 parts by weight with respect to 100 parts by weight of the resin component).
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.

<Talc>
The resin composition of the present invention may contain talc. In this invention, it exists in the tendency for the plating performance of the part irradiated with the laser to improve by mix | blending talc.
The talc used in the present invention is also preferably talc surface-treated with at least one compound selected from polyorganohydrogensiloxanes and organopolysiloxanes. In this case, the adhesion amount of the siloxane compound is preferably 0.1 to 5% by weight of talc.
When the resin composition of this invention contains a talc, it is preferable that the compounding quantity of a talc is 1-30 weight part with respect to 100 weight part of resin components, and 2-10 weight part is more preferable. When talc is surface-treated, the total amount of the surface-treated is preferably within the above range.

<Phosphazene compound>
The resin composition of the present invention contains a phosphazene compound. By blending a phosphazene compound, flame retardancy can be improved.
The phosphazene compound is an organic compound having —P═N— bond in the molecule, and preferably a cyclic phosphazene compound represented by the following general formula (1) and a chain phosphazene represented by the following general formula (2). A compound, and at least one selected from the group consisting of a crosslinked phosphazene compound in which at least one phosphazene compound selected from the group consisting of the following general formula (1) and the following general formula (2) is crosslinked by a crosslinking group It is a compound of this.

式（１）中、ａは３〜２５の整数であり、Ｒ¹及びＲ²は、同一又は異なっていてもよく、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリロキシ基、アミノ基、ヒドロキシ基、アリール基又はアルキルアリール基を示す。

In the formula (1), a is an integer of 3 to 25, R ¹ and R ² may be the same or different, and an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an allyloxy group, an amino group, A hydroxy group, an aryl group or an alkylaryl group is shown.

式（２）中、ｂは３〜１００００の整数であり、Ｒ³及びＲ⁴は、同一又は異なっていてもよく、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリロキシ基、アミノ基、ヒドロキシ基、アリール基又はアルキルアリール基を示す。
Ｒ⁵は、−Ｎ＝Ｐ（ＯＲ³）₃基、−Ｎ＝Ｐ（ＯＲ⁴）₃基、−Ｎ＝Ｐ（Ｏ）ＯＲ³基、−Ｎ＝Ｐ（Ｏ）ＯＲ⁴基から選ばれる少なくとも１種を示し、Ｒ⁶は、−Ｐ（ＯＲ³）₄基、−Ｐ（ＯＲ⁴）₄基、−Ｐ（Ｏ）（ＯＲ³）₂基、−Ｐ（Ｏ）（ＯＲ⁴）₂基から選ばれる少なくとも１種を示す。

In the formula (2), b is an integer of ^{3 to} 10000, R ³ and R ⁴ may be the same or different, and an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an allyloxy group, an amino group, A hydroxy group, an aryl group or an alkylaryl group is shown.
R ⁵ is selected from —N═P (OR ³ ) ₃ group, —N═P (OR ⁴ ) ₃ group, —N═P (O) OR ³ group, —N═P (O) OR ⁴ group. At least one type is shown, and R ⁶ is —P (OR ³ ) ₄ group, —P (OR ⁴ ) ₄ group, —P (O) (OR ³ ) ₂ group, —P (O) (OR ⁴ ) _2. At least one selected from the group is shown.

  In the above formulas (1) and (2), examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group. In general, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group and the like are preferable, and a methyl group is preferable. C1-C4 alkyl groups such as ethyl group and propyl group are particularly preferred.

  Examples of the cycloalkyl group include cycloalkyl groups having 5 to 14 carbon atoms such as a cyclopentyl group and a cyclohexyl group, and among them, a cycloalkyl group having 5 to 8 carbon atoms is preferable.

  Examples of the alkenyl group include alkenyl groups having 2 to 8 carbon atoms such as vinyl group and allyl group. Examples of the cycloalkenyl group include cycloalkenyl groups having 5 to 12 carbon atoms such as cyclopentyl group and cyclohexyl group. Is mentioned.

  As an alkynyl group, aryls, such as C2-C8 alkynyl groups, such as an ethynyl group and a propynyl group, an ethynylbenzene group, etc. are mentioned, for example.

  Examples of the aryl group include aryl groups having 6 to 20 carbon atoms such as a phenyl group, a methylphenyl (ie, tolyl) group, a dimethylphenyl (ie, xylyl) group, a trimethylphenyl group, and a naphthyl group. Among them, an aryl group having 6 to 10 carbon atoms is preferable, and a phenyl group is particularly preferable.

  Examples of the alkylaryl group include aralkyl groups having 6 to 20 carbon atoms such as benzyl group, phenethyl group, and phenylpropyl group. Among them, aralkyl groups having 7 to 10 carbon atoms are preferable, and benzyl group is particularly preferable. .

Among these, those in which R ¹ and R ² in the general formula (1) and R ³ and R ⁴ in the general formula (2) are an aryl group and an arylalkyl group are preferable. By using such an aromatic phosphazene, the thermal stability of the resin composition can be effectively increased. From such a viewpoint, R ¹ , R ² , R ³ and R ⁴ are more preferably aryl groups, and particularly preferably phenyl groups.

  Examples of the cyclic and / or chain phosphazene compounds represented by the general formulas (1) and (2) include (polyoxyphosphazene, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene, etc. ) (Poly) xylyloxyphosphazenes such as tolyloxyphosphazene, o, m-xylyloxyphosphazene, o, p-xylyloxyphosphazene, m, p-xylyloxyphosphazene, o, m, p-trimethylphenyloxy (Poly) phenoxytolyloxyphosphazenes such as phosphazenes, phenoxy o-tolyloxyphosphazenes, phenoxy m-tolyloxyphosphazenes, phenoxy p-tolyloxyphosphazenes, phenoxy o, m-xylyloxyphosphazenes, phenoxy o, p-xy (Poly) phenoxytolyloxyxylyloxyphosphazene, phenoxy o, m, p-trimethylphenyloxyphosphazene, etc. can be exemplified, preferably cyclic and / or chain phenoxy Such as phosphazene.

As the cyclic phosphazene compound represented by the general formula (1), cyclic phenoxyphosphazene in which R ¹ and R ² are phenyl groups is particularly preferable. Examples of such a cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene, octachlorocyclohexane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting with a phenoxy group. . The cyclic phenoxyphosphazene compound is preferably a compound in which a in the general formula (1) is an integer of 3 to 8, and may be a mixture of compounds having different a.

  The average a is preferably 3-5, more preferably 3-4. In particular, a mixture of compounds in which a = 3 is 50% by weight or more, a = 4 is 10 to 40% by weight, and a = 5 or more is 30% by weight or less in total.

As the chain phosphazene compound represented by the general formula (2), chain phenoxyphosphazene in which R ³ and R ⁴ are phenyl groups is particularly preferable. Such a chain phenoxyphosphazene compound is obtained by, for example, subjecting hexachlorocyclotriphosphazene obtained by the above-mentioned method to reversion polymerization at a temperature of 220 to 250 ° C., and obtaining a linear dichlorophosphazene having a polymerization degree of 3 to 10,000. Examples include compounds obtained by substitution with a phenoxy group. B in the general formula (2) of the linear phenoxyphosphazene compound is preferably 3 to 1000, more preferably 3 to 100, and still more preferably 3 to 25.

  Examples of the bridged phosphazene compound include a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (that is, a bisphenol S residue) and a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. Compounds having a crosslinked structure of 4,4′-diphenylene group, such as compounds having a crosslinked structure of 4,4′-oxydiphenylene group, compounds having a crosslinked structure of 4,4′-thiodiphenylene group, etc. Etc.

In addition, as the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound in which a cyclic phenoxyphosphazene compound in which R ¹ and R ² are phenyl groups in the general formula (1) is crosslinked by the above-mentioned crosslinking group, or the above general formula (2) In the above, a crosslinked phenoxyphosphazene compound in which a chain phenoxyphosphazene compound in which R ³ and R ⁴ are phenyl groups is crosslinked by the crosslinking group is preferable from the viewpoint of flame retardancy, and the cyclic phenoxyphosphazene compound is crosslinked by the crosslinking group. A crosslinked phenoxyphosphazene compound is more preferable.
The content of the phenylene group in the crosslinked phenoxyphosphazene compound is such that the cyclic phosphazene compound represented by the general formula (1) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (2) and The amount is usually 50 to 99.9% by weight, preferably 70 to 90% by weight, based on the number of phenylene groups. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  In the present invention, the phosphazene compound is a crosslinked phenoxy obtained by crosslinking the cyclic phenoxyphosphazene compound represented by the general formula (1) and the cyclic phenoxyphosphazene compound represented by the general formula (1) with a crosslinking group. In view of the flame retardancy and mechanical properties of the resin composition, at least one selected from the group consisting of phosphazene compounds is preferable.

The compounding quantity of a phosphazene compound is 10-30 weight part with respect to 100 weight part of resin components, 12-28 weight part is preferable and 15-25 weight part is especially preferable.
The resin composition of the present invention may contain only one type of phosphazene compound, or may contain two or more types. When two or more types are included, the total amount falls within the above range.

<Polytetrafluoroethylene>
The resin composition of the present invention contains polytetrafluoroethylene (PTFE). As polytetrafluoroethylene, polytetrafluoroethylene having fibril forming ability is preferable. Polytetrafluoroethylene having fibril-forming ability is classified as type 3 according to the ASTM standard. Examples of polytetrafluoroethylene having fibril-forming ability include Teflon (registered trademark) 6-J manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and Polyflon F201L, FA500B, FA500C manufactured by Daikin Chemical Industries, Ltd. . Examples of the aqueous dispersion of polytetrafluoroethylene include Fluon D-1 manufactured by Daikin Chemical Industries, Ltd. and polytetrafluoroethylene compounds having a multilayer structure formed by polymerizing vinyl monomers. Any type can be used for the resin composition of the present invention.

  In order to further improve the appearance of a molded article obtained by injection molding a resin composition containing polytetrafluoroethylene, a specific coated polytetrafluoroethylene (hereinafter referred to as coated polytetrafluoroethylene and coated with an organic polymer) is used. May be abbreviated). The specific coated polytetrafluoroethylene is one in which the content ratio of polytetrafluoroethylene in the coated polytetrafluoroethylene falls within the range of 40 to 95% by weight, of which 43 to 80% by weight, and further 45 It is preferable to be -70 wt%, particularly 47-60 wt%. As the specific coated polytetrafluoroethylene, for example, Metablene A-3800, A-3700, KA-5503 manufactured by Mitsubishi Rayon Co., Poly TS AD001 manufactured by PIC Co., etc. can be used.

The compounding quantity of polytetrafluoroethylene is 0.1-1 weight part with respect to 100 weight part of resin components, 0.2-0.9 weight part is more preferable, 0.3-0.8 weight part is Particularly preferred. In the case of coated polytetrafluoroethylene, the amount added corresponds to the amount of pure polytetrafluoroethylene. When the blending amount of polytetrafluoroethylene is less than 0.1 parts by weight, the flame retardant effect is insufficient. On the other hand, when it exceeds 1 part by weight, appearance of the molded product may be deteriorated.
The resin composition of the present invention may contain only one type of polytetrafluoroethylene or two or more types. When two or more types are included, the total amount falls 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 0.5-5 weight part with respect to 100 weight part of resin components, and contains 1.0-4 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.

<Organic phosphorus stabilizer>
The resin composition of the present invention 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 0.05 to 1 part by weight with respect to 100 parts by weight of the resin component. More preferred is 0.08 to 0.5 parts by weight. 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.

  In the present invention, it is particularly preferable to mix 0.01-1 part by weight of monostearyl acid phosphate and / or distearyl acid phosphate as an organophosphorus stabilizer with respect to 100 parts by weight of the polycarbonate resin. It is more preferable to contain -0.5 weight part. By making it 0.01 parts by weight or more, the decomposition of the polycarbonate resin can be remarkably suppressed, and by making it 1 parts by weight or less, it is possible to improve the adhesion with the glass fiber and to remarkably improve the mechanical strength. it can.

  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.

  In the present invention, it is particularly preferable to add 0.01 to 0.5 parts by weight of monostearyl acid phosphate and / or distearyl acid phosphate as an organophosphorus stabilizer with respect to 100 parts by weight of the resin component. More preferably, it contains 1 to 0.5 parts by weight. By making it 0.01 parts by weight or more, decomposition of the polycarbonate resin can be remarkably suppressed, and by making it 0.5 parts by weight or less, adhesion with glass fibers is improved and mechanical strength is remarkably improved. be able to.

<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 this antioxidant is 0.01-5 weight part with respect to 100 weight part of resin components, 0.05-3 weight Part is more preferred.
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 this mold release agent is 0.01-5 weight part with respect to 100 weight part of resin components, and 0.05-3 weight part. Part is more preferred.
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.

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, ultraviolet absorbers, inorganic fillers, 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.

In the present invention, the phosphazene compound is preferably blended as a master batch or as a specific granular phosphazene. Specifically, the following aspects are illustrated.
(First aspect)
As a first aspect, it is obtained by melt-kneading 40 to 65% by weight of an aromatic polycarbonate resin (A) having a weight average molecular weight of 15,000 to 55000 and 35 to 60% by weight of an aromatic phosphazene compound (B). A flame retardant masterbatch characterized in that the total of component (A) and component (B) is 95 to 100% by weight. By setting it as such a structure, the workability at the time of melt-kneading with resin is excellent, and also when it mix | blends with a thermoplastic resin, the flame retardant masterbatch excellent in a flame retardance and a mechanical physical property is obtained.
(Second embodiment)
A second embodiment is a flame retardant master batch obtained by melt-kneading an aromatic polycarbonate resin (A) having a weight average molecular weight of 5,000 to 55,000 and an aromatic phosphazene compound (B) in a pressure kneader. is there. By setting it as such a structure, the flame retardant masterbatch which can express a flame retardance and a mechanical physical property effectively and stably is obtained.

(Third embodiment)
As a 3rd aspect, a total of 100 weight part of aromatic polycarbonate resin (A) 85-20 weight% and aromatic phosphazene compound (B) 15-80 weight%, and fluoropolymer (C) are 0.005-2. It is a flame retardant masterbatch obtained by melting and kneading parts by weight. By setting it as such a structure, the workability at the time of melt-kneading with resin is excellent, and also when it mix | blends with a thermoplastic resin, the flame retardant masterbatch excellent in a flame retardance and a mechanical physical property is obtained.

(Fourth aspect)
As a fourth aspect, the proportion on the sieve having an opening of 400 μm is 55% by weight or more, and the bulk density is 0.3 to 1.5 g / ml, which is blended into the resin as a granular phosphazene compound. It is an aspect. The phosphazene compound is finely powdered at room temperature, but has the property of solidifying against compression and shearing. If this is done, the phosphazene compound adheres to the extruder screw when melt-kneaded with a thermoplastic resin in an extruder. However, the use of the granular phosphazene compound makes it difficult to cause problems such as sticking to the extruder screw.

(Fifth aspect)
To the phosphazene compound (A), a polycarbonate resin granule (B) having a ratio of passing through a sieve having an opening of 1000 μm is 30% by weight or more, and a weight ratio of (A) / (B) is 85/15 to 5 / It is an aspect which mix | blends with resin as a granular phosphazene compound characterized by being mixed by 95 and having a bulk density of 0.4-1.5 g / ml. By adopting such a configuration, the productivity is excellent, and the workability at the time of melt-kneading with the thermoplastic resin is also excellent.

  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. A metal component in which copper, nickel, gold, silver, and palladium are mixed is preferable, and 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, in particular, 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 component>
S-3000FN: manufactured by Mitsubishi Engineering Plastics, polycarbonate resin AT-08: manufactured by Nippon A & L, ABS resin

<Elastomer>
S-2030: Mitsubishi Rayon, Si elastomer: Methyl methacrylate / methyl acrylate / dimethylsiloxane copolymer

<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, almost equimolar mixture of mono- and di-stearyl acid phosphate

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

<Polytetrafluoroethylene>
6-J: manufactured by Mitsui DuPont Fluorochemical Co., Ltd., a fluoropolymer having fibril forming ability

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

<Phosphazene compound>
FP-100: manufactured by Fushimi Pharmaceutical Co., Ltd., phenoxyphosphazene compound

<Glass fiber>
T-187: manufactured by Nippon Electric Glass Co., Ltd., glass fiber having an average fiber length / average fiber diameter of more than 10, an average fiber length of 3 mm, an average fiber diameter of 13 μm, and a glass fiber having a circular cross section (flatness ratio 1)
MF-SR: Asahi fiberglass, glass fiber (short fiber) having an average fiber length / average fiber diameter of 10 or less, an average fiber length of 50 μm, an average fiber diameter of 10 μm, a glass fiber having a circular cross section (flatness 1)

<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.

<Flame retardance (UL94V)>
After drying the pellets obtained by the above-mentioned manufacturing method at 120 ° C. for 5 hours, injection was performed under the conditions of a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. using a J50-EP type injection molding machine manufactured by Nippon Steel. A UL test specimen having a length of 125 mm, a width of 13 mm, and a thickness of 1.6 mm was molded.

  The flame retardancy of each resin composition was evaluated by conditioning the test piece for UL test obtained by the above-mentioned method for 48 hours in a temperature-controlled room at a temperature of 23 ° C. and a humidity of 50%, and US Underwriters Laboratories. The test was conducted in accordance with the UL94 test (combustion test of plastic materials for equipment parts) defined by (UL). UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in the following table.

  Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied.

<Bending elastic modulus and bending strength>
After drying the pellets obtained by the above-described production method at 120 ° C. for 5 hours, using Nissei Plastic Industries, SG75-MII, under conditions of a cylinder temperature of 300 ° C., a mold temperature of 100 ° C., and a molding cycle of 50 seconds. Injection molding was performed to form a 4 mm thick ISO tensile test piece.
Based on ISO178, the bending elastic modulus (unit: MPa) and bending strength (unit: MPa) were measured at a temperature of 23 ° C. using the above ISO tensile test piece (4 mm thickness).

<Charpy impact strength>
Using the ISO tensile test piece (4 mm thickness) obtained above, the Charpy impact strength with notch was measured under the condition of 23 ° C. in accordance with ISO 179.

<Load deflection temperature (DTUL)>
Using the ISO tensile test piece (4 mm thickness) obtained above, the deflection temperature under load was measured under the condition of a load of 1.80 MPa in accordance with ISO75-1 and ISO75-2.

<Plating properties>
After drying the pellets of each Example and each Comparative Example obtained by the above-described production method at 100 ° C. for 5 hours, the cylinder temperature was 280 ° C. and the mold temperature was 80 using SG75-MII manufactured by Nissei Plastic Industry. Injection molding was performed at a temperature of 50 ° C. and a molding cycle of 50 seconds to form a 3 mm thick plate.
A 1064 nm YAG laser was used for the 3 mm-thick plate obtained above, and the output was any of 2.6 to 13 W, the speed was 1 to 2 m / s, and the frequency was in the range of 10 to 50 μs. After printing with laser irradiation under various conditions combined, the test piece was degreased with sulfuric acid, treated with THP Alkali Acti and THP Alkali Acce manufactured by Kizai Co., Ltd., and then plated with a SEL copper manufactured by Kizai Co., Ltd. went. The test pieces after the plating treatment were visually judged and classified into the following five stages.
5: Among various laser conditions, the condition where the plating is clearly mounted is 75 to 100%.
4: Among various laser conditions, the condition where the plating is clearly mounted is 50 to 74%.
3: Of various laser conditions, the condition where the plating is clearly mounted is 30 to 49%.
2: Among various laser conditions, the condition where the plating is clearly mounted is 10 to 29%.
1: Under various laser conditions, the condition where the plating is clearly placed is less than 10%.

The results are shown in the table below.

  As is apparent from the above table, when the composition of the present invention is used, while maintaining the plating property, it is effective in various mechanical properties such as bending elastic modulus, bending strength, Charpy impact strength and deflection temperature under load, and flame retardancy. Excellent specimens were obtained. On the other hand, when the blending amount of the polycarbonate resin is small (Comparative Example 1), the blending amount of the glass fiber having an average fiber length / average fiber diameter of 10 or less is outside the range of the present invention (Comparative Example). 2, 3) The flame retardancy was inferior.

Claims (16)

5 to 40 parts by weight of glass fiber having an average fiber length / average fiber diameter of 10 or less, and 0.5 to elastomer for 100 parts by weight of a resin component containing 65 to 90% by weight of polycarbonate resin and 35 to 10% by weight of styrene resin 10 to 10 parts by weight, laser direct structuring additive 5 to 10 parts by weight containing antimony and tin, 10 to 30 parts by weight of a phosphazene compound and 0.1 to 1 part by weight of polytetrafluoroethylene 0.1 to 1 part by weight of resin composition for laser direct structuring object. The resin composition of Claim 1 whose compounding quantity of the said glass fiber whose said average fiber length / average fiber diameter is 10 or less is 5-30 weight part with respect to 100 weight part of said resin components. Furthermore, 0.5-5 weight part of titanium oxide is contained with respect to 100 weight part of said resin components, The resin composition of Claim 1 or 2 characterized by the above-mentioned. The resin composition according to any one of claims 1 to 3, wherein the component having the largest blending amount among the metal components contained in the laser direct structuring additive is tin. The resin composition according to any one of claims 1 to 4, wherein the laser direct structuring additive contains 90% by weight or more of tin oxide and 3 to 8% by weight of antimony oxide. The resin according to any one of claims 1 to 5, wherein the laser direct structuring additive contains 0.01 to 0.1% by weight of lead oxide and / or 0.001 to 0.01% by weight of copper oxide. Composition. The resin composition according to claim 1, wherein the elastomer is a siloxane copolymer elastomer. 8. The glass fiber having an average fiber length / average fiber diameter of more than 10 is contained at a ratio of 100% by weight or less of the blend amount of glass fibers having an average fiber length / average fiber diameter of 10 or less. 2. The resin composition according to item 1. The resin molded product formed by shape | molding the resin composition of any one of Claims 1-8. The resin molded product according to claim 9, wherein the evaluation of the UL-94 test of the resin molded product at a thickness of 1.6 mm is V-0. The resin molded product according to claim 9 or 10, which has a plating layer on a surface of the resin molded product. The resin molded product according to claim 11 , wherein the plating layer retains performance as an antenna. The resin molded product according to any one of claims 9 to 12 , which is a portable electronic device component. A plating layer comprising forming a plating layer by applying a metal to a surface of a resin molded product obtained by molding the resin composition according to any one of claims 1 to 8 after laser irradiation. Manufacturing method of resin-molded products. The manufacturing method of the resin molded product with a plating layer of Claim 14 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 14 or 15.

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