WO2015053159A1

WO2015053159A1 - Resin composition, resin molded article, and method for producing resin molded article

Info

Publication number: WO2015053159A1
Application number: PCT/JP2014/076358
Authority: WO
Inventors: 庄司　英和
Original assignee: 三菱エンジニアリングプラスチックス株式会社
Priority date: 2013-10-07
Filing date: 2014-10-02
Publication date: 2015-04-16

Abstract

Provided is a resin composition having superior fire retardance and mechanical characteristics such as flexural modulus of elasticity, flexural strength, Charpy impact strength, and deflection temperature under load while maintaining platability. The resin composition, which is for laser direct structuring, contains, for every 100 parts by mass of components including 40-95 mass% of a resin component and 5-60 mass% of fiberglass, 0.5-10 parts by mass of an elastomer, 5-20 parts by mass of a laser direct structuring additive containing copper and chromium, 5-30 parts by mass of at least one fire retardant selected from a phosphazene compound and a condensed phosphate ester, and 0.1-1 parts by mass of polytetrafluoroethylene. The resin component contains 65-90 mass% of a polycarbonate resin and 35-10 mass% of a styrene resin.

Description

Resin composition, resin molded product, and method for producing resin molded product

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.

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

Here, if glass fiber is added to improve mechanical properties, the flame retardancy tends to be inferior. In addition, as a result of examination by the present inventors, it was found that the flame retardancy is also affected by the type of LDS additive. In particular, the LDS additive is necessary for forming the plating, but can be a foreign matter in the resin molded product. The present invention aims to solve such problems of the prior art, and maintains various plating properties while maintaining various plating properties such as flexural modulus, flexural strength, Charpy impact strength and deflection temperature under load. It aims at providing the resin composition excellent in the flame retardance.

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> Laser direct structuring additive 5 to 20 containing 0.5 to 10 parts by mass of elastomer, copper and chromium with respect to 100 parts by mass of resin component 40 to 95% by mass and glass fiber 5 to 60% by mass Including at least one flame retardant selected from 5 parts by mass, a phosphazene compound and a condensed phosphate ester, and 0.1 to 1 part by mass of polytetrafluoroethylene,
A resin composition for laser direct structuring, wherein the resin component comprises 65 to 90% by mass of a polycarbonate resin and 35 to 10% by mass of a styrene resin.
<2> The resin composition for laser direct structuring according to <1>, wherein the flame retardant includes a phosphazene compound.
<3> The resin composition for laser direct structuring according to <2>, wherein the phosphazene compound is phenoxyphosphazene.
<4> The glass fiber has an oblateness ratio of 1.5 or less indicated by a major axis / minor axis ratio (D2 / D1) where the major axis of the cross section perpendicular to the length direction is D2 and the minor axis is D1. <2> or <3> The resin composition for laser direct structuring as described in <3>.
<5> In the glass fiber, the flatness indicated by the ratio of major axis / minor axis (D2 / D1) when the major axis of the cross section perpendicular to the length direction is D2 and the minor axis is D1 exceeds 1.5. The resin composition for laser direct structuring according to <2> or <3>, which is 0.0 or less.
<6> The flame retardant contains a condensed phosphate ester,
The glass fiber has a flatness ratio of more than 1.5 and not more than 8.0 expressed by a ratio of major axis / minor axis (D2 / D1) where D2 is a major axis of a cross section perpendicular to the length direction and D1 is a minor axis. The resin composition for laser direct structuring according to <1>.
<7> The resin composition for laser direct structuring according to any one of <1> to <6>, wherein the laser direct structuring additive is a spinel structure.
<8> The resin composition for laser direct structuring according to any one of <1> to <7>, wherein the elastomer is a siloxane copolymer elastomer.
<9> A resin molded product obtained by molding the resin composition for laser direct structuring 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 an average 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 <11>, wherein the plated layer has performance as an antenna.
<13> The resin molded product according to any one of <9> to <12>, which is a portable electronic device part.
<14> The surface of a resin molded product obtained by molding the resin composition for laser direct structuring according to any one of <1> to <8> is irradiated with a laser, and then a metal is applied to form a plating layer. The manufacturing method of the resin molded product with a plating layer including forming.
<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 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. .

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 of the present invention is a laser direct structuring containing 0.5 to 10 parts by weight of an elastomer, copper and chromium with respect to 100 parts by weight of a component containing 40 to 95% by weight of a resin component and 5 to 60% by weight of glass fiber. Containing 5 to 20 parts by mass of an additive, 5 to 30 parts by mass of a flame retardant selected from a phosphazene compound and a condensed phosphate ester, and 0.1 to 1 part by mass of polytetrafluoroethylene, It contains 65 to 90% by mass of polycarbonate resin and 35 to 10% by mass of styrene resin. By using such a resin composition for LDS, higher plating properties can be achieved.
A preferred first embodiment of the resin composition of the present invention is an aspect in which the flame retardant contains a phosphazene compound.
In a second preferred embodiment of the resin composition of the present invention, the flame retardant contains a condensed phosphate ester, and the glass fiber has a major axis D2 and a minor axis D1 in a cross section perpendicular to the length direction. The aspect ratio indicated by the ratio of major axis / minor axis (D2 / D1) is more than 1.5 and not more than 8.0.
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, 65 to 85% by weight of polycarbonate resin and 35 to 15% by weight of styrene resin. Is more preferable. The resin component may contain other resin components. However, the other resin is preferably 5% by mass 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 aromatic polycarbonate, aliphatic polycarbonate, and 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 and the like are preferable, and bisphenol A is preferable. 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 polycarbonate resins 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 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, with respect to the polycarbonate resin used in the present invention, for example, the description in paragraph numbers 0018 to 0066 of JP2012-072338A can be referred to, and the contents thereof are incorporated in the present 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.

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 styrenic 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 esters, phenyl acrylate, benzyl acrylate, etc. Methacrylic acid aryl esters such as acid aryl esters, phenyl methacrylate and benzyl methacrylate, epoxy group-containing acrylic acid esters or methacrylic acid esters such as glycidyl acrylate and glycidyl methacrylate, maleimides such as N, N-methylmaleimide and N-phenylmaleimide Examples thereof include α-, β-unsaturated carboxylic acids such as acrylic monomers, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid and itaconic acid, or anhydrides thereof.

Further, rubbery polymers that can be copolymerized with styrene monomers include polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, acrylonitrile-butadiene random copolymers and block copolymers, acrylonitrile. -Butadiene copolymers, copolymers of alkyl acrylates or alkyl methacrylates and butadiene, polybutadiene-polyisoprene diene copolymers, ethylene-isoprene random copolymers and block copolymers, ethylene-butene randoms 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, Ethylene-propylene-non-conjugated diene terpolymers such as tylene-vinyl acetate copolymer, ethylene-propylene-hexadiene copolymer, acrylic rubber, composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate or methacrylate rubber, etc. 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 A combination (AES resin) is preferable, 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, acrylonitrile-butadiene-styrene copolymer (ABS resin) which is particularly preferably used is a thermoplastic graft copolymer obtained by graft copolymerization of acrylonitrile and styrene with a butadiene rubber component, and a copolymer of acrylonitrile and styrene. It is a mixture of The butadiene rubber component is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and particularly preferably 13 to 25% by mass in 100% by mass 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 mass or more of the total composition is preferably a resin component, more preferably 50% by mass or more is a resin component, and 60% by mass or more is a resin component. Is more preferable.

<Glass fiber>
The resin composition of the present invention contains glass fibers.
A 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.
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 form of the glass fiber is “glass roving” in which single fibers or a plurality of twisted strands are continuously wound, “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, as the glass fiber, either a circular cross-sectional shape or a modified cross-sectional shape is preferable. Here, the cross-sectional shape is distinguished by 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. The flatness in the present invention is the average flatness.
In the present invention, from the viewpoint of low warpage, glass fibers having a flatness ratio of more than 1.5 and not more than 8.0 are preferable, glass fibers having a flatness ratio of 2.0 to 6.0 are more preferable, and a flatness ratio of 2.0 to 6.0 is preferable. 4.0 glass fiber is more preferred. Regarding such flat glass, the description of paragraph numbers 0065 to 0072 of JP-A-2011-195820 can be referred to, and the contents thereof are incorporated in the present specification.
In the present invention, the major axis D2 is preferably 18-30 μm, and the minor axis D1 is preferably 5-12 μm.
On the other hand, from the viewpoint of improving the weld strength, a glass fiber with a flatness ratio of 1.5 or less is preferable, a glass fiber with a flatness ratio of 1.3 or less is more preferable, a glass fiber with a flatness ratio of 1.1 or less is more preferable, and the flatness ratio is 1 glass fiber is particularly preferred.

The glass fiber may be surface-treated with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like. The amount is usually 0.01 to 1% by mass 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.

The compounding amount of the glass fiber in the resin composition of the present invention is 5 to 60% by mass, preferably 15 to 60% by mass, preferably 15 to 55% by mass when the total amount of the resin component and the glass fiber is 100% by mass. % Is more preferable, and 20 to 50% by mass is further preferable. By setting it as such a range, higher plating property can be achieved.
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.
In the resin composition of the present invention, it is usually preferable that the resin component and the glass fiber occupy 70% by mass 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. Examples of the elastomer used in the present invention include methyl methacrylate-butadiene-styrene copolymer (MBS resin), methyl methacrylate-butadiene rubber copolymer (MB resin), and styrene-butadiene triblock called SBS and SEBS. Copolymer and its hydrogenated product, styrene-isoprene triblock copolymer called SPS and SEPS and its hydrogenated product, olefinic thermoplastic elastomer called TPO, polyester elastomer, siloxane Examples thereof include rubber, acrylate rubber, and siloxane copolymer elastomer. As the elastomer, elastomers described in paragraph numbers 0075 to 0088 of JP2012-251061A, elastomers 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 siloxane copolymer elastomer is more preferable.

The elastomer used in the present invention is preferably a graft copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith. The production method of the graft copolymer may be any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft.

The rubber component 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, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethyl hexyl acrylate copolymer, and polyorganosiloxane rubber. Silicone rubber, butadiene-acrylic composite rubber, IPN (Interpenetrating Polymer Network) type composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber, etc. And ethylene-α-olefin rubber, ethylene-acrylic rubber, fluororubber, and the like. These may be used alone or in admixture of two or more. Among these, in terms of mechanical properties and surface appearance, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferable. .

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, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable. A compound. 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 a core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and around it. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing (meth) acrylic acid ester is particularly preferred. The core / shell type graft copolymer preferably contains 40% by mass or more of a rubber component, and more preferably contains 60% by mass or more. Moreover, what contains 10 mass% or more of (meth) acrylic acid is preferable. The core / shell type in the present invention does not necessarily have to be clearly distinguishable between the core layer and the shell layer, and widely includes compounds obtained by graft polymerization of a rubber component around the core portion. It is the purpose.

Preferred 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- Styrene copolymer, methyl methacrylate- (acryl / silicone IPN rubber) copolymer, silicone-acrylic composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate Polyorganosiloxane polyalkyl (meth) silicone containing acrylate - acrylic composite rubber and methyl methacrylate - butadiene copolymer (MB) is particularly preferred. Such rubbery polymers may be used alone or in combination of two or more.

Examples of such elastomers include “Paraloid (registered trademark, the same applies hereinafter) EXL2602”, “Paraloid EXL2603”, “Paraloid EXL2655”, “Paraloid EXL2311”, “Paraloid EXL2313” manufactured by Rohm and Haas Japan. , “Paraloid EXL2315”, “Paraloid KM330”, “Paraloid KM336P”, “Paraloid KCZ201”, “Metabrene (registered trademark, the same applies hereinafter) C-223A”, “Metabrene E-901”, “Metabrene S” manufactured by Mitsubishi Rayon Co., Ltd. -2001 "," Metabrene SRK-200 "," Metabrene S-2030 "" Kane Ace (registered trademark, the same applies hereinafter) M-511 "," Kane Ace M-600 "," Kane Ace M-400 "," Kane Ace M-400 "," Kane Ace -580 "," Kane Ace M-711 "," Kane Ace MR-01 ", manufactured by Ube Industries, Ltd. of" UBESTA XPA ", and the like.

The blending amount of the elastomer is 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and further preferably 1.5 to 5 parts by mass with respect to 100 parts by mass of the component including the resin component and the glass fiber. 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 resin composition of the present invention includes an LDS additive containing copper and chromium. By using an LDS additive containing copper and chromium, flame retardancy and plating properties can be improved.
The LDS additive in the present invention is obtained by adding 4 parts by mass of an additive considered to be an LDS additive to 100 parts by mass of polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, Iupilon (registered trademark), S-3000F) at 1064 nm. YAG laser is used to print by laser irradiation under any of the conditions of output 2.6 to 13 W, speed 1 to 2 m / s, frequency 10 to 50 μs, and then test This refers to a compound capable of forming a plating when a piece is degreased with sulfuric acid, treated with THP alkaline acti and THP alkaline acce manufactured by Kizai, and then plated with a SEL copper manufactured by Kizai. 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 LDS additive in the present invention is not particularly limited as long as it contains copper and chromium. The LDS additive in the present invention preferably contains 10 to 30% by mass of copper. Further, it is preferable to contain 15 to 50% by mass of chromium.
The LDS additive in the present invention is preferably an oxide containing copper and chromium.

The LDS additive in the present invention is preferably a spinel structure. A spinel structure is one of the typical crystal structure types found in double oxide AB ₂ O ₄ type compounds (A and B are metal elements). That is, in the present invention, a spinel structure which is an oxide containing copper and chromium is more preferable.

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

The particle size of the LDS additive is preferably 0.01 to 50 μm, 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 blending amount of the LDS additive is 5 to 20 parts by mass, preferably 6 to 15 parts by mass, and more preferably 8 to 13 parts by mass with respect to 100 parts by mass of the component including the resin component and the glass fiber. When the blending amount is 20 parts by mass or more, the impact property is lowered, the polycarbonate resin in the resin component is decomposed, or the flame retardancy is inferior.
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 falls within the above range.

<Flame Retardant>
The resin composition of the present invention contains at least one flame retardant selected from phosphazene compounds and condensed phosphate esters.
The blending amount of the flame retardant is 5 to 30 parts by weight, preferably 6 to 25 parts by weight, more preferably 10 to 20 parts by weight, with respect to 100 parts by weight of the component including the resin component and the glass fiber. Part is particularly preferred.
The resin composition of the present invention may contain only one type of at least one flame retardant selected from phosphazene compounds and condensed phosphate esters, or may contain two or more types.
Specifically, an embodiment that includes only one or two or more phosphazene compounds and does not include a condensed phosphate ester, an embodiment that includes only one or two or more condensed phosphate esters, and does not include a hofphazene compound, The aspect containing 2 or more types of phosphazene compounds and 1 type, or 2 or more types of condensed phosphate ester is mentioned.
When 2 or more types of flame retardants are included, the total amount is in 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, preferably a cyclic phosphazene compound represented by the following general formula (1), 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.

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.

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 groups, —N═P (OR ⁴ ) ₃ groups, —N═P (O) OR ³ groups, and —N═P (O) OR ⁴ groups. R ⁶ represents at least one type, and R ⁶ represents —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. An alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group and a hexyl group. Particularly preferred are alkyl groups having 1 to 4 carbon atoms such as ethyl group and propyl group.

Examples of the cycloalkyl group include a cycloalkyl group having 5 to 14 carbon atoms such as a cyclopentyl group and a cyclohexyl group, among which 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.

Examples of the alkynyl group include alkynyl groups having 2 to 8 carbon atoms such as ethynyl group and propynyl group, and aryl such as ethynylbenzene group.

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. Of these, 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, for example, (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 phosphazene, phenoxy o-tolyloxyphosphazene, phenoxy m-tolyloxyphosphazene, phenoxy p-tolyloxyphosphazene, phenoxy o, m-xylyloxyphosphazene, phenoxy o, p-ki Examples include (poly) phenoxytolyloxyxylyloxyphosphazene, phenoxy o, m, p-trimethylphenyloxyphosphazene, etc., 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 cyclic phenoxyphosphazene compounds include hexachlorocyclotriphosphazene, octachlorochloromethane, 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 to 5, more preferably 3 to 4. Of these, a mixture of compounds in which a = 3 is 50% by mass or more, a = 4 is 10 to 40% by mass, and a = 5 or more is 30% by mass 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 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. In the general formula (2), b in 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, and compounds having a crosslinked structure of 4,4′-thiodiphenylene group 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 Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. 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.

<< Condensed phosphate ester >>
The resin composition of the present invention contains a condensed phosphate ester. Flame retardance can be improved by blending the condensed phosphate ester.
The condensed phosphate ester is preferably represented by the following general formula (1).

General formula (1)

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom or an organic group, except that R ₁ , R ₂ , R ₃ and R ₄ are all hydrogen atoms. X represents a divalent organic group, p is 0 or 1, q represents an integer of 1 or more, and r represents 0 or an integer of 1 or more.)

In the above general formula (1), examples of the organic group include an alkyl group, a cycloalkyl group, and an aryl group, which may or may not have a substituent, and the substituent includes an alkyl group, an alkoxy group, and an alkylthio group. Aryl group, aryloxy group, arylthio group, halogen atom, halogenated aryl group and the like. Further, a group in which these substituents are combined, or a group in which these substituents are combined by combining with an oxygen atom, a sulfur atom, a nitrogen atom, or the like may be used. The divalent organic group refers to a divalent or higher group formed by removing one carbon atom from the above organic group. Examples thereof include an alkylene group, a phenylene group, a substituted phenylene group, and a polynuclear phenylene group derived from bisphenols.

Specific examples of the condensed phosphate ester represented by the general formula (1) include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, Tricresyl phenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) Phosphate, bis (2,3-dibromopropyl) -2,3-dichlorophosphate, bis (chloropropyl) monooctyl phosphate, bisphenol A tetraphenyl phosphate DOO, bisphenol A tetra cresyl diphosphate, bisphenol A tetra xylylene distearate phosphate, hydroquinone tetraphenyl diphosphate, hydroquinone tetra cresyl phosphate, various ones such as hydroquinone tetra xylylene distearate phosphate are exemplified.
Examples of commercially available condensed phosphate esters include “CR733S” (resorcinol bis (diphenyl phosphate)), “CR741” (bisphenol A bis (diphenyl phosphate)), “PX-200” from Daihachi Chemical Industry Co., Ltd. (Resorcinol bis (dixylenyl phosphate)), “Adekastab FP-700” (2,2-bis (p-hydroxyphenyl) propane / trichlorophosphine oxide polycondensate (polymerization degree 1 to 4) from Asahi Denka Kogyo Co., Ltd. It is sold under the trade name such as 3) phenol condensate and is readily available.

<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, and 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 a polytetrafluoroethylene compound having a multilayer structure obtained by polymerizing a vinyl monomer. 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 mass, of which 43 to 80% by mass, and further 45 It is preferable that the amount is ˜70% by mass, particularly 47 to 60% by mass. As the specific coated polytetrafluoroethylene, for example, Metablene A-3800, A-3700, KA-5503 manufactured by Mitsubishi Rayon Co., Ltd., PolyＰTS AD001 manufactured by PIC Co., etc. can be used.

The blending amount of polytetrafluoroethylene is 0.1 to 1 part by weight, more preferably 0.2 to 0.8 part by weight, with respect to 100 parts by weight of the component containing the resin component and glass fiber. 0.6 parts by weight 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 mass, the flame retardant effect is insufficient. On the other hand, when it exceeds 1 part by mass, the 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.

<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 in paragraphs 0073 to 0095 of JP2009-35691A 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, which may be the same or different. M is an integer of 0 to 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- More preferred are a ditert-butylphenyl group, a 2,4-ditert-butylmethylphenyl group, and a tolyl group.

Of these, phosphate esters represented by the following general formula (3 ') are preferred.

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.

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, trioctyl phosphite , Trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, monobutyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol phosphite Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, etc. Triesters of acid, 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 with respect to 100 parts by weight of the component containing the resin component and the glass fiber. -1.0 part by mass is more preferable, 0.08-0.5 part by mass is more preferable, and 0.08-0.3 part by mass is particularly preferable. By setting it as 0.01 mass part or more, decomposition | disassembly of polycarbonate resin by an LDS additive can be suppressed more effectively, By making it 5 mass parts or less, the adhesive strength of glass fiber and a polycarbonate is raised, The strength can be further improved.

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

In the present invention, monostearyl acid phosphate and / or distearyl acid phosphate as an organophosphorus stabilizer is preferably 5 parts by mass or less, more preferably 1 part by mass or less based on 100 parts by mass of the resin component and glass fiber. Preferably, 0.5 parts by mass or less is more preferable, 0.3 parts by mass or less is particularly preferable, and 0.25 parts by mass or less is more preferable. Moreover, as a lower limit, 0.01 mass part or more is preferable, 0.05 mass part or more is more preferable, and 0.08 or more is further more preferable.
By setting it as 0.01 mass part or more, decomposition | disassembly of polycarbonate resin can be suppressed notably, By making it 0.5 mass part or less, adhesiveness with glass fiber is improved and mechanical strength is improved notably. 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 Tilethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane and the like. Among them, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is preferable.
When the resin composition of the present invention contains an antioxidant, the blending amount of the antioxidant is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the component containing the resin component and the glass fiber. 0.05 to 3 parts by mass 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 falls 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 the present invention contains a release agent, the compounding amount of the release agent is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the component containing the resin component and the glass fiber. 0.05 to 3 parts by mass 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 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, ultraviolet absorbers, inorganic fillers, fluorescent whitening agents, anti-dripping agents, antistatic agents, antifogging agents, lubricants, antiblocking agents, fluidity improvers, Plasticizers, dispersants, antibacterial agents and the like can be mentioned. Two or more of these may be used in combination.
Regarding these components, descriptions in JP2007-314766A, JP2008-127485A, JP2009-51989A, JP2012-72338A, and the like can be referred to, and the contents thereof are described in the present 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)
The first embodiment is obtained by melt-kneading 40 to 65% by mass of an aromatic polycarbonate resin (A) having a mass average molecular weight of 15000 to 55000 and 35 to 60% by mass of an aromatic phosphazene compound (B). Examples of the flame retardant masterbatch are characterized in that the sum of the component (A) and the component (B) is 95 to 100% by mass. 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 masterbatch obtained by melting and kneading an aromatic polycarbonate resin (A) having a mass 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 third embodiment, a total of 100 parts by mass of the aromatic polycarbonate resin (A) 85 to 20% by mass and the aromatic phosphazene compound (B) 15 to 80% by mass, and the fluoropolymer (C) is 0.005 to 2%. It is a flame retardant masterbatch obtained by melt-kneading a mass part. 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 mass or more, and the bulk density is 0.3 to 1.5 g / ml, which is added to 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 particle (B) having a ratio of passing through a sieve having an opening of 1000 μm is 30% by mass or more, and a mass ratio of (A) / (B) is 85/15 to 5 / 95, and is blended into the resin as a granular phosphazene compound characterized by having a bulk density of 0.4 to 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 a resin molded product from the resin composition of the present invention is not particularly limited, and a molding method generally employed for thermoplastic resins, that is, a general injection molding method, an 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, molding method using rapid heating mold, 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 and the like can be employed. A molding method using a hot runner method can also be selected.

The resin molded product with a plated layer of the present invention includes forming a plated layer by applying a metal to the surface of a resin molded product formed by molding the resin composition of the present invention after laser irradiation.
Hereafter, the process of providing a plating layer on the surface of the resin molded product which shape | molded the resin composition of this invention is demonstrated according 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. The resin molded product in the present invention is preferably used for parts of portable electronic devices, vehicles and medical devices, and electronic parts including other electric circuits. In particular, the resin molded product of the present invention has both high impact resistance, rigidity, and excellent heat resistance, as well as low anisotropy and low warpage, so that it can be used in electronic notebooks, portable computers, etc. It is extremely effective as an internal structure and casing such as a PDA, a pager, a mobile phone, and a PHS. In particular, the resin molded product is suitable for flat plate-like parts having an average thickness excluding ribs of 1.2 mm or less (the lower limit is not particularly defined, for example, 0.4 mm or more). Particularly suitable as a housing.
Further, it is suitable for applications in which the evaluation of the UL-94 test of resin molded products having an average thickness of 1.6 mm is required to be 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 preferred wavelength range is 200 nm to 1200 nm. Particularly preferred is 800 to 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. Such a circuit is preferably used as an antenna of a portable electronic device component. That is, as an example of a preferred embodiment of the resin molded product of the present invention, a plating layer (preferably a copper plating layer) provided on the surface of the resin molded product of the present invention (preferably a portable electronic device component) is an antenna. Resin molded products possessing the performance as described above.

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-3000F: Mitsubishi Engineering Plastics, polycarbonate resin AT-08: Nippon A & L, ABS resin

<Glass fiber>
T-187: manufactured by Nippon Electric Glass Co., Ltd., glass fiber having a circular cross section with a diameter of 13 μm and a cut length of 3 mm (flatness ratio 1)
3PA-820: manufactured by Nitto Boseki Co., Ltd., glass fiber having a flat cross section with a diameter of 28 μm and a short diameter of 7 μm (flatness ratio 4)
3PL-820: manufactured by Nitto Boseki Co., Ltd., glass fiber having a flat cross section with a diameter of 20 μm and a short diameter of 10 μm (flatness ratio 2)

<LDS additive>
Black 1G: Copper chrome oxide of spinel structure manufactured by Shepard Japan

<Elastomer>
S-2030: Mitsubishi Rayon Co., Ltd. Methyl Methacrylate / Methyl Acrylate / Dimethylsiloxane Copolymer M711: Kaneka Co., Ltd. Core / shell type elastomer comprising a butadiene core and an acrylic shell

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

<Condensed phosphate ester>
PX-200: manufactured by Daihachi Chemical Industry Co., Ltd., resorcinol bis-2,6-xylenyl phosphate FP-700: manufactured by Asahi Denka Kogyo Co., Ltd., ADK STAB FP-700, 2,2-bis (p-hydroxyphenyl) Phenol condensate of propane / trichlorophosphine oxide polycondensate (degree of polymerization 1 to 3)

<PTFE>
6-J: Fluoropolymer having a fibril forming ability manufactured by Mitsui DuPont Fluorochemicals

<Phosphorus stabilizer>
AX-71: ADEKA, (mono and distearyl acid phosphate) mixture of approximately equimolar <antioxidant>
Irg1076: Irganox 1076, manufactured by BASF, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate <release agent>
VPG861: manufactured by Cognis Oleochemicals Japan, pentaerythritol tetrastearate

<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 (UL-94 test)>
After drying the pellets obtained by the above-mentioned production method at 120 ° C. for 5 hours, using a J50-EP type injection molding machine manufactured by Nippon Steel Works under the conditions of a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. A test piece for UL test having a length of 125 mm, a width of 13 mm, and an average thickness of 1.6 mm was formed by injection molding.

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 afterflame 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 afterflame time is the length of time for which the test piece continues to burn with flame 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) as not satisfying V-2.

<Bending elastic modulus and bending strength>
After the pellets obtained by the above-mentioned production method were dried at 120 ° C. for 5 hours, using SG75-MII manufactured by Nissei Plastic Industry, the cylinder temperature was 300 ° C., the mold temperature was 100 ° C., and the molding cycle was 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 property (LDS activity)-Placing Index>
After the pellets obtained by the above-mentioned production method were dried at 120 ° C. for 5 hours, using SG75-MII manufactured by Nissei Plastic Industry, the cylinder temperature was 280 ° C., the mold temperature was 80 ° C., and the molding cycle was 50 seconds. Injection molding was performed 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 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 placed is 50 to 74%
3: Among various laser conditions, the condition where the plating is clearly mounted is 30 to 49%
2: 10 to 29% of the various laser conditions are clearly plated
1: Under various laser conditions, the condition where the plating is clearly placed is less than 10%.

<Warpage>
The pellets obtained by the above-described production method were dried at 120 ° C. for 5 hours, and then injection molded using NEX80 manufactured by Nissei Plastic Industry under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 100 ° C., and a molding cycle of 40 seconds. Then, a disk of 0.8 mm thickness × diameter 100 mm filled with one side gate was formed. After molding, a test piece was placed on the flat plate, and the height of the most lifted from the flat plate due to warpage was measured to obtain the amount of warpage (mm).

The results are shown in the table below.

As is apparent from the above table, when the composition of the present invention is used (Examples 1-1 to 1-9), the bending elastic modulus, bending strength, Charpy impact strength, deflection temperature under load, etc. are maintained while maintaining plating properties. Test pieces excellent in various mechanical properties and flame retardancy were obtained. On the other hand, when the amount of the flame retardant was small (Comparative Example 1-1), the flame retardancy was poor. Further, when the amount of the LDS additive was small (Comparative Example 1-2), the plating property was inferior. Further, it was found that even when the necessary amounts of the flame retardant and the LDS additive were blended, the flame retardancy was inferior when the proportion of the ABS resin was large (Comparative Example 1-3). It was also found that the warpage was particularly small when glass fibers having a flat cross section were used (Examples 1-4, 1-7 to 1-9).

As is apparent from the above table, when the composition of the present invention is used, while maintaining the plating property, it has various mechanical properties such as bending elastic modulus, bending strength, Charpy impact strength and deflection temperature under load, and flame retardancy. Excellent test pieces were obtained (Examples 2-1 to 2-12). On the other hand, when the compounding amount of the LDS additive was small (Comparative Example 2-1), the flame retardancy was excellent, but the plating property was inferior. On the other hand, when the blending amount of the polycarbonate resin was small (Comparative Example 2-2), the plating property was excellent but the flame retardancy was inferior. It was also found that the warpage was particularly small when glass fibers having a flat cross section were used (Examples 2-7 to 2-12).

Claims

For 100 parts by mass of the component containing 40 to 95% by mass of the resin component and 5 to 60% by mass of the glass fiber,
0.5 to 10 parts by weight of an elastomer, 5 to 20 parts by weight of a laser direct structuring additive containing copper and chromium, 5 to 30 parts by weight of at least one flame retardant selected from phosphazene compounds and condensed phosphates, and poly Containing 0.1-1 part by weight of tetrafluoroethylene,
A resin composition for laser direct structuring, wherein the resin component comprises 65 to 90% by mass of a polycarbonate resin and 35 to 10% by mass of a styrene resin.
The resin composition for laser direct structuring according to claim 1, wherein the flame retardant comprises a phosphazene compound.
The resin composition for laser direct structuring according to claim 2, wherein the phosphazene compound is phenoxyphosphazene.
The flatness indicated by the major axis / minor axis ratio (D2 / D1) when the major axis of the cross section perpendicular to the length direction is D2 and the minor axis is D1 is 1.5 or less. 2. The resin composition for laser direct structuring according to 2 or 3.
The glass fiber has a flatness ratio of more than 1.5 and not more than 8.0 expressed by a ratio of major axis / minor axis (D2 / D1) where D2 is a major axis of a cross section perpendicular to the length direction and D1 is a minor axis. The resin composition for laser direct structuring according to claim 2 or 3, wherein
The flame retardant comprises a condensed phosphate ester;
The glass fiber has a flatness ratio of more than 1.5 and not more than 8.0 expressed by a ratio of major axis / minor axis (D2 / D1) where D2 is a major axis of a cross section perpendicular to the length direction and D1 is a minor axis. The resin composition for laser direct structuring according to claim 1, wherein
The resin composition for laser direct structuring according to any one of claims 1 to 6, wherein the laser direct structuring additive is a spinel structure.
The resin composition for laser direct structuring according to any one of claims 1 to 7, wherein the elastomer is a siloxane copolymer elastomer.
A resin molded product obtained by molding the resin composition for laser direct structuring according to any one of claims 1 to 8.
The resin molded product according to claim 9, wherein the evaluation of the UL-94 test of the resin molded product at an average 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 part.
A plating layer is formed by applying a metal to a surface of a resin molded product obtained by molding the resin composition for laser direct structuring according to any one of claims 1 to 8 after irradiating a laser. The manufacturing method of the resin molded product with a plating layer containing.
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.