WO2014115475A1 - Resin composition for laser direct structuring, molded resin article, and method of manufacturing molded resin article having plating film - Google Patents

Resin composition for laser direct structuring, molded resin article, and method of manufacturing molded resin article having plating film Download PDF

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Publication number
WO2014115475A1
WO2014115475A1 PCT/JP2013/084780 JP2013084780W WO2014115475A1 WO 2014115475 A1 WO2014115475 A1 WO 2014115475A1 JP 2013084780 W JP2013084780 W JP 2013084780W WO 2014115475 A1 WO2014115475 A1 WO 2014115475A1
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mass
resin composition
group
laser direct
resin
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PCT/JP2013/084780
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French (fr)
Japanese (ja)
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庄司　英和
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三菱エンジニアリングプラスチックス株式会社
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Priority to JP2014519737A priority Critical patent/JP5615992B1/en
Priority to CN201380071268.8A priority patent/CN104955896B/en
Publication of WO2014115475A1 publication Critical patent/WO2014115475A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2251—Oxides; Hydroxides of metals of chromium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0236—Plating catalyst as filler in insulating material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/09—Shape and layout
    • H05K2201/09009—Substrate related
    • H05K2201/09118—Moulded substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/09—Shape and layout
    • H05K2201/09818—Shape or layout details not covered by a single group of H05K2201/09009 - H05K2201/09809
    • H05K2201/0999—Circuit printed on or in housing, e.g. housing as PCB; Circuit printed on the case of a component; PCB affixed to housing
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
    • H05K2203/107—Using laser light
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
    • H05K3/185—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method by making a catalytic pattern by photo-imaging

Definitions

  • the present invention relates to a resin composition for laser direct structuring (hereinafter sometimes simply referred to as “resin composition”). Furthermore, it is related with the manufacturing method of the resin molded product formed by shape
  • LDS laser direct structuring
  • the present invention aims to solve the problems of the prior art, and maintains various plating properties while maintaining various plating properties such as bending elastic modulus, bending strength, Charpy impact strength and deflection temperature under load, and the like. It aims at providing the resin composition excellent in the flame retardance.
  • Laser direct structuring additive 5 to 20 containing 0.5 to 10 parts by weight of elastomer, copper and chromium with respect to 100 parts by weight of a component containing 40 to 95% by weight of polycarbonate resin and 5 to 60% by weight of glass fiber Parts by weight, phosphorus flame retardant 5 to 30 parts by weight, and polytetrafluoroethylene 0.1 to 1 part by weight,
  • the elastomer has an acrylonitrile / butadiene / styrene copolymer content of less than 10% by mass of the total, The content of the acrylonitrile / butadiene / styrene copolymer is less than 10% by mass of the total amount of the polycarbonate resin and the acrylonitrile / butadiene / styrene copolymer.
  • Resin composition for laser direct structuring ⁇ 2> The resin composition for laser direct structuring according to ⁇ 1>, wherein the phosphorus flame retardant is a condensed phosphate ester. ⁇ 3> The resin composition for laser direct structuring according to ⁇ 1>, wherein the phosphorus flame retardant is a phosphazene compound. ⁇ 4> The resin composition for laser direct structuring according to any one of ⁇ 1> to ⁇ 3>, wherein the laser direct structuring additive is a spinel structure. ⁇ 5> The resin composition for laser direct structuring according to any one of ⁇ 1> to ⁇ 4>, wherein the elastomer is a siloxane copolymer elastomer.
  • ⁇ 6> 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 of the glass fiber is D2 and the minor axis is D1 is 1.5 or less.
  • ⁇ 7> 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 of the glass fiber is D2 and the minor axis is D1 exceeds 1.5.
  • the resin composition for laser direct structuring according to any one of ⁇ 1> to ⁇ 6> which is 0 or less.
  • ⁇ 8> The resin composition for laser direct structuring according to any one of ⁇ 1> to ⁇ 7>, wherein the composition does not substantially contain an acrylonitrile / butadiene / styrene copolymer.
  • ⁇ 10> The resin molded product according to ⁇ 9>, further having a plating layer on the surface.
  • ⁇ 11> The resin molded product according to ⁇ 9> or ⁇ 10>, which is a portable electronic device part.
  • ⁇ 12> The resin molded product according to ⁇ 10> or ⁇ 11>, wherein the plated layer has performance as an antenna.
  • ⁇ 13> 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.
  • 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 ⁇ 13> or ⁇ 14>.
  • 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. .
  • FIG. 1 indicates a resin molded product
  • 2 indicates a laser
  • 3 indicates a portion irradiated with the laser
  • 4 indicates a plating solution
  • 5 indicates a plating layer.
  • the resin composition of the present invention is a laser direct structuring containing 0.5 to 10 parts by mass of an elastomer, copper and chromium with respect to 100 parts by mass of a component containing 40 to 95% by mass of a polycarbonate resin and 5 to 60% by mass of glass fiber.
  • the elastomer contains 5 to 20 parts by mass of an additive, 5 to 30 parts by mass of a phosphorus-based flame retardant, and 0.1 to 1 part by mass of polytetrafluoroethylene, and the elastomer has a content of acrylonitrile / butadiene / styrene copolymer.
  • the total content of the acrylonitrile / butadiene / styrene copolymer is less than 10% by mass, and the content of the acrylonitrile / butadiene / styrene copolymer is less than 10% by mass of the total amount of the polycarbonate resin and the acrylonitrile / butadiene / styrene copolymer.
  • 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.
  • 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.
  • 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, you may use the polycarbonate resin manufactured through the process of adjusting the amount of OH groups of a terminal group, after passing through the manufacturing process of a general melting method in this invention.
  • 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.
  • the resin composition of the present invention may contain only one type of polycarbonate resin, or may contain two or more types.
  • the proportion of the polycarbonate resin in all resin components is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more. .
  • the resin composition of the present invention may contain, for example, a polyamide resin, a polyester resin, a styrene resin, etc. in addition to the polycarbonate resin.
  • the blending amount of these resins is preferably less than 10% by mass of the resin component, more preferably 5% by mass or less, and further preferably 3% by mass or less.
  • the blending amount of acrylonitrile / butadiene / styrene copolymer (ABS resin) is less than 10 mass% of the total amount of the polycarbonate resin and acrylonitrile / butadiene / styrene copolymer.
  • ABS resin here includes, for example, an ABS resin that can be contained in an elastomer or the like to be described later.
  • 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 ⁇ m. 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.
  • the glass fiber either a circular cross-sectional shape or a modified cross-sectional shape is preferable.
  • 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.
  • glass fibers having a flatness ratio of more than 1.5 and 8 or less are preferable, glass fibers having a flatness ratio of 2 to 6 are more preferable, and glass fibers having a flatness ratio of 2 to 4 are more preferable.
  • 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 ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, and the like.
  • a silane coupling agent such as ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, and the like.
  • the amount is usually 0.01 to 1% by mass of the glass fiber.
  • 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,
  • the compounding amount of the glass fiber in the resin composition of the present invention is 5% by mass or more, preferably 8% by mass or more, preferably 10% by mass or more when the total amount of the polymer bonate resin and the glass fiber is 100% by mass. More preferably, it is 60% by mass or less, more preferably 55% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less.
  • 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.
  • the resin composition of the present invention contains an elastomer.
  • the elastomer By containing the elastomer, the impact resistance of the resin composition can be improved.
  • the elastomer used in the present invention include methyl methacrylate-butadiene-styrene copolymer (MBS resin), styrene-butadiene triblock copolymer called SBS, SEBS, and hydrogenated products thereof, SPS, SEPS, Styrene-isoprene triblock copolymer and its hydrogenated product, olefinic thermoplastic elastomer called TPO, polyester elastomer, siloxane rubber, acrylate rubber, siloxane copolymer elastomer, etc.
  • MFS resin methyl methacrylate-butadiene-styrene copolymer
  • SEBS styrene-butadiene triblock copolymer
  • TPO olefinic thermoplastic elasto
  • 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.
  • an MBS resin or a siloxane copolymer elastomer is particularly preferably used, and a siloxane copolymer elastomer is more preferable.
  • the elastomer used in the present invention has an acrylonitrile / butadiene / styrene copolymer content of less than 10% by mass, preferably 5% by mass or less, and more preferably 3% by mass or less.
  • 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.
  • 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 dimethylsiloxane units as constituent units is preferable.
  • 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.
  • 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, and may be crosslinked with a siloxane-based crosslinking agent. Moreover, there is no restriction
  • JP 2012-131934 A The description in paragraphs [0055] to [0080] of JP 2012-131934 A can be referred to, and the contents thereof 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 ⁇ m, and even more preferably 100 nm to 3 ⁇ m.
  • the polyalkyl (meth) acrylate used in the production of the silicone-acrylic composite rubber is a polymer containing alkyl (meth) acrylate units.
  • alkyl (meth) acrylate examples 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.
  • the polyalkyl (meth) acrylate may be a copolymer containing a polyfunctional monomer unit as a constituent component.
  • 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 isocyanate.
  • Examples include nurate. These can be used alone or in combination of two or more.
  • the content in the case of using a polyfunctional monomer is not particularly limited, but it is preferably 0.1 to 2% by mass in 100% by mass of polyalkyl (meth) acrylate, and 0.3 to 1 More preferably, it is mass%.
  • the content of the polyfunctional monomer is 0.1% by mass 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.
  • the content is 2% by mass or less, the impact strength tends to be further improved.
  • 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 “Methbrene S series” by Mitsubishi Rayon Co., for example, “S-2030” or the like is used. It is preferable.
  • the blending amount of the elastomer is 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, and more preferably 2 to 6 parts by weight with respect to 100 parts by weight of the component including the polycarbonate resin 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.
  • the resin composition of the present invention includes an LDS additive containing copper and chromium.
  • 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 ⁇ s, 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 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).
  • the LDS additive may contain a trace amount of other metals in addition to copper and chromium.
  • other metals include antimony, tin, lead, indium, iron, cobalt, nickel, zinc, cadmium, silver, bismuth, arsenic, manganese, magnesium, calcium, and the like, and manganese is preferable. These metals may exist as oxides.
  • An example of a preferred embodiment of the present invention is an LDS additive in which the content of metal oxides other than copper chromium oxide is 10% by mass or less.
  • the particle size of the LDS additive is preferably 0.01 to 50 ⁇ m, more preferably 0.05 to 30 ⁇ m.
  • 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 polycarbonate resin and the glass fiber.
  • 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.
  • the composition of the present invention contains a phosphorus-based flame retardant.
  • the phosphorus-based flame retardant is preferably a condensed phosphate ester compound and / or a phosphazene compound.
  • the compounding amount of the phosphorus-based flame retardant is 5 to 30 parts by mass, preferably 8 to 25 parts by mass, and particularly preferably 10 to 20 parts by mass with respect to 100 parts by mass of the component including the polycarbonate resin and the glass fiber.
  • the resin composition of the present invention may contain only one type of phosphorus-based flame retardant, or may contain two or more types. When two or more types are included, the total amount falls within the above range.
  • Condensed phosphate ester can improve a flame retardance by mix
  • the condensed phosphate ester is preferably represented by the following general formula (1).
  • 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.
  • 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.
  • 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.
  • 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,
  • condensed phosphate esters examples 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 (degree of polymerization 1 to It is sold under the trade name such as 3) phenol condensate and is readily available.
  • the resin composition of this invention can improve a flame retardance by mix
  • 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.
  • 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.
  • 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.
  • 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.
  • cycloalkyl group examples 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.
  • alkenyl group examples include alkenyl groups having 2 to 8 carbon atoms such as vinyl group and allyl group.
  • cycloalkenyl group examples include cycloalkenyl groups having 5 to 12 carbon atoms such as cyclopentyl group and cyclohexyl group. Is mentioned.
  • alkynyl group examples include alkynyl groups having 2 to 8 carbon atoms such as ethynyl group and propynyl group, and aryl such as ethynylbenzene group.
  • aryl group examples 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.
  • a phenyl group having 6 to 10 carbon atoms is preferable, and a phenyl group is particularly preferable.
  • alkylaryl group examples 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. .
  • 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.
  • 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
  • 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 cycl
  • 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.
  • chain phosphazene compound represented by the general formula (2) chain phenoxyphosphazene in which R 3 and R 4 are phenyl groups is particularly preferable.
  • 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.
  • b in the linear phenoxyphosphazene compound is preferably 3 to 1000, more preferably 3 to 100, and still more preferably 3 to 25.
  • bridged phosphazene compound examples 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.
  • 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)
  • 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.
  • 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.
  • at least one selected from the group consisting of phosphazene compounds is preferable.
  • the resin composition of the present invention contains polytetrafluoroethylene (PTFE).
  • PTFE 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. .
  • aqueous dispersion of polytetrafluoroethylene examples 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.
  • 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.
  • 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 polycarbonate resin and glass fiber. 0.6 parts by weight is particularly preferred.
  • the amount added corresponds to the amount of pure polytetrafluoroethylene.
  • 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.
  • the resin composition of the present invention preferably contains an organic phosphorus stabilizer.
  • 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.
  • 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).
  • 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.
  • phosphate esters represented by the following general formula (3 ') are preferred.
  • R ′ is an alkyl group having 2 to 25 carbon atoms, which may be the same or different.
  • m ′ is 1 or 2.
  • 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.
  • phosphate esters examples 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.
  • 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.
  • R ′ is an alkyl group, an alkyl group having 1 to 30 carbon atoms is preferable.
  • R ′ is an aryl group, an aryl group having 6 to 30 carbon atoms is preferable.
  • 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,
  • 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 polycarbonate resin and glass fiber.
  • 05 to 0.3 parts by mass is more preferable, and 0.08 to 0.25 parts by mass is even more preferable.
  • 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 phosphorous stabilizer, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • 0.01 to 0.5 parts by mass of monostearyl acid phosphate and / or distearyl acid phosphate as an organophosphorus stabilizer is added to 100 parts by mass of the polycarbonate resin and the glass fiber.
  • 0.05 to 0.3 parts by mass is included, and 0.08 to 0.25 parts by mass is particularly preferable.
  • the resin composition of the present invention may contain an antioxidant.
  • an antioxidant a phenolic antioxidant is preferable, and more specifically, 2,6-di-butyl-4-methylphenol, n-octadecyl-3- (3,5-di-t-butyl- 4′-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-tert-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-di
  • the resin composition of the present invention contains an antioxidant, the 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 polycarbonate resin and 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 is preferably within the above range.
  • 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.
  • aliphatic carboxylic acid examples include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid.
  • the term “aliphatic carboxylic acid” is used to include alicyclic 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.
  • 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.
  • the same aliphatic carboxylic acid as that described above can be used.
  • the alcohol component constituting the aliphatic carboxylic acid ester examples 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.
  • the aliphatic alcohol also includes an alicyclic alcohol.
  • 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.
  • aliphatic carboxylic acid ester examples 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.
  • the compounding amount of the release agent is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of a component containing a polycarbonate resin and 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 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.
  • 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 polycarbonate 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 and 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.
  • various mixers such as a tumbler and Henschel mixer, and then melt kneaded with a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc.
  • the phosphazene compound is preferably blended as a master batch or as a specific granular phosphazene.
  • the first embodiment is obtained by melt-kneading 40 to 65% by mass of an aromatic polycarbonate resin (A) having a weight 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.
  • a second embodiment is a flame retardant masterbatch obtained by melting and 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.
  • a second embodiment is a flame retardant masterbatch obtained by melting and 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.
  • 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
  • the proportion on the sieve having an opening of 400 ⁇ m 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.
  • 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.
  • a polycarbonate resin particle (B) having a ratio of passing through a sieve having an opening of 1000 ⁇ m 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.
  • 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.
  • 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.
  • the resin molded product 1 is a flat substrate.
  • 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.
  • the resin molded product is not limited to the final product, and includes various parts.
  • 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.
  • 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.
  • 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 YGA laser is preferable.
  • 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.
  • 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.
  • the plating layer 5 is formed only in the portion irradiated with the laser.
  • 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 resin molded product in which a plating layer provided on the surface of a portable electronic device component has performance as an antenna can be mentioned.
  • ⁇ LDS additive> Black1G: manufactured by Shepard Japan, a component other than spinel copper chrome oxide, copper chrome oxide, 1% by mass or less 24-3588 PK: manufactured by Ferro, a component other than spinel structured copper chrome oxide, copper chrome oxide 1% by mass or less 24-3097PK: manufactured by Ferro, containing 5-7% by mass of spinel copper chrome oxide and manganese oxide
  • ⁇ PTFE> 6-J Mitsui Dupont Fluoro Chemical Co., Ltd., fluoropolymer having fibril forming ability
  • AX-71 Almost equimolar mixture of mono- and di-stearyl acid phosphate (manufactured by ADEKA)
  • Irg1076 manufactured by BASF, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate
  • VPG861 manufactured by Cognis Oleochemicals Japan, pentaerythritol tetrastearate
  • ⁇ Flame retardancy (UL94)> The pellets obtained by the above production method were dried at 120 ° C. for 5 hours, and then injected using a J50-EP injection molding machine manufactured by Nippon Steel, under the conditions of a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. A UL test specimen having a length of 125 mm, a width of 13 mm, and a thickness of 0.8 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 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.
  • 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. Furthermore, if any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) as not satisfying V-2.
  • test piece 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%.
  • 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.

Abstract

Provided is a resin composition having consistent plating properties as well as exceptional flame retardancy and various mechanical properties such as bending modulus, bending strength, Charpy impact strength, and deflection temperature under load. A resin composition for laser direct structuring containing, with respect to 100 parts by mass of a component containing 40 to 95% by mass of a polycarbonate resin and 5 to 60% by mass of glass fiber, 0.5 to 10 parts by mass of an elastomer, 5 to 20 parts by mass of a laser direct structuring additive containing copper and chromium, 5 to 30 parts by mass of a phosphorus-based flame retardant, and 0.1 to 1 parts by mass of polytetrafluoroethylene. The elastomer contains less than 10% by mass of acrylonitrile/butadiene/styrene copolymer, and the amount of acrylonitrile/butadiene/styrene copolymer is less than 10% by mass of the total polycarbonate resin and acrylonitrile/butadiene/styrene copolymer content.

Description

レーザーダイレクトストラクチャリング用樹脂組成物、樹脂成形品、およびメッキ層付樹脂成形品の製造方法Resin composition for laser direct structuring, resin molded product, and method for producing resin molded product with plating layer
　本発明は、レーザーダイレクトストラクチャリング用樹脂組成物（以下、単に、「樹脂組成物」ということがある）に関する。さらに、該樹脂組成物を成形してなる樹脂成形品および、該樹脂成形品の表面に、メッキ層を形成したメッキ層付樹脂成形品の製造方法に関する。 The present invention relates to a resin composition for laser direct structuring (hereinafter sometimes simply referred to as “resin composition”). Furthermore, it is related with the manufacturing method of the resin molded product formed by shape | molding this resin composition, and the resin molded product with a plating layer which formed the plating layer on the surface of this resin molded product.
　近年、スマートフォンを含む携帯電話の開発に伴い、携帯電話の内部にアンテナを製造する方法が種々検討されている。特に、携帯電話に３次元設計ができるアンテナを製造する方法が求められている。このような３次元アンテナを形成する技術の１つとして、レーザーダイレクトストラクチャリング（以下、「ＬＤＳ」ということがある）技術が注目されている。ＬＤＳ技術は、例えば、ＬＤＳ添加剤を含む樹脂成形品の表面にレーザーを照射し、レーザーを照射した部分のみを活性化させ、該活性化させた部分に金属を適用することによってメッキ層を形成する技術である。この技術の特徴は、接着剤などを使わずに、樹脂基材表面に直接にアンテナ等の金属構造体を製造できる点にある。かかるＬＤＳ技術は、例えば、特許文献１～３等に開示されている。 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 3.
国際公開ＷＯ２０１１／０９５６３２号パンフレットInternational publication WO2011 / 095632 pamphlet 国際公開ＷＯ２０１１／０７６７２９号パンフレットInternational Publication WO2011 / 076729 Pamphlet 国際公開ＷＯ２０１１／０７６７３０号パンフレットInternational Publication WO2011 / 077630 Pamphlet
　ここで、機械的特性を向上させるためにガラス繊維を配合しようとすると、難燃性が劣る傾向にある。また、本発明者が検討したところ、ＬＤＳ添加剤の種類によっても、難燃性に影響が出ることが分かった。本発明はかかる従来技術の問題点を解決することを目的としたものであって、メッキ性を維持しつつ、曲げ弾性率、曲げ強度、シャルピー衝撃強さや荷重たわみ温度などの各種機械的特性および難燃性に優れた樹脂組成物を提供することを目的とする。 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. The present invention aims to solve the problems of the prior art, and maintains various plating properties while maintaining various plating properties such as bending elastic modulus, bending strength, Charpy impact strength and deflection temperature under load, and the like. It aims at providing the resin composition excellent in the flame retardance.
　かかる状況のもと、本発明者が鋭意検討を行った結果、下記の手段＜１＞により、好ましくは＜２＞～＜１５＞により、上記課題は解決された。 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 <15>.
＜１＞ポリカーボネート樹脂４０～９５質量％およびガラス繊維５～６０質量％を含む成分１００質量部に対し、エラストマー０．５～１０質量部、銅およびクロムを含むレーザーダイレクトストラクチャリング添加剤５～２０質量部、リン系難燃剤５～３０質量部、ならびに、ポリテトラフルオロエチレン０．１～１質量部を含み、
前記エラストマーは、アクリロニトリル／ブタジエン／スチレン共重合体の含有量が全体の１０質量％未満であり、
アクリロニトリル／ブタジエン／スチレン共重合体の含有量は、ポリカーボネート樹脂とアクリロニトリル／ブタジエン／スチレン共重合体の合計量の１０質量％未満である、
レーザーダイレクトストラクチャリング用樹脂組成物。
＜２＞前記リン系難燃剤が、縮合リン酸エステルである、＜１＞に記載のレーザーダイレクトストラクチャリング用樹脂組成物。
＜３＞前記リン系難燃剤が、ホスファゼン化合物である、＜１＞に記載のレーザーダイレクトストラクチャリング用樹脂組成物。
＜４＞前記レーザーダイレクトストラクチャリング添加剤が、スピネル構造体である、＜１＞～＜３＞のいずれかに記載のレーザーダイレクトストラクチャリング用樹脂組成物。
＜５＞前記エラストマーが、シロキサン共重合エラストマーである、＜１＞～＜４＞のいずれかに記載のレーザーダイレクトストラクチャリング用樹脂組成物。
＜６＞前記ガラス繊維の長さ方向に直角な断面の長径をＤ２、短径をＤ１とするときの長径／短径比（Ｄ２／Ｄ１）で示される扁平率が１．５以下である、＜１＞～＜５＞のいずれかに記載のレーザーダイレクトストラクチャリング用樹脂組成物。
＜７＞前記ガラス繊維の長さ方向に直角な断面の長径をＤ２、短径をＤ１とするときの長径／短径比（Ｄ２／Ｄ１）で示される扁平率が１．５を超え８．０以下である、＜１＞～＜６＞のいずれかに記載のレーザーダイレクトストラクチャリング用樹脂組成物。
＜８＞前記組成物が、アクリロニトリル／ブタジエン／スチレン共重合体を実質的に含まない、＜１＞～＜７＞のいずれかに記載のレーザーダイレクトストラクチャリング用樹脂組成物。
＜９＞＜１＞～＜８＞のいずれかに記載のレーザーダイレクトストラクチャリング用樹脂組成物を成形してなる樹脂成形品。
＜１０＞さらに、表面にメッキ層を有する、＜９＞に記載の樹脂成形品。
＜１１＞携帯電子機器部品である、＜９＞または＜１０＞に記載の樹脂成形品。
＜１２＞前記メッキ層がアンテナとしての性能を保有する、＜１０＞または＜１１＞に記載の樹脂成形品。
＜１３＞＜１＞～＜８＞のいずれかに記載のレーザーダイレクトストラクチャリング用樹脂組成物を成形してなる樹脂成形品の表面に、レーザーを照射後、金属を適用して、メッキ層を形成することを含む、メッキ層付樹脂成形品の製造方法。
＜１４＞前記メッキが銅メッキである、＜１３＞に記載のメッキ層付樹脂成形品の製造方法。
＜１５＞＜１３＞または＜１４＞に記載のメッキ層付樹脂成形品の製造方法を含む、アンテナを有する携帯電子機器部品の製造方法。 <1> Laser direct structuring additive 5 to 20 containing 0.5 to 10 parts by weight of elastomer, copper and chromium with respect to 100 parts by weight of a component containing 40 to 95% by weight of polycarbonate resin and 5 to 60% by weight of glass fiber Parts by weight, phosphorus flame retardant 5 to 30 parts by weight, and polytetrafluoroethylene 0.1 to 1 part by weight,
The elastomer has an acrylonitrile / butadiene / styrene copolymer content of less than 10% by mass of the total,
The content of the acrylonitrile / butadiene / styrene copolymer is less than 10% by mass of the total amount of the polycarbonate resin and the acrylonitrile / butadiene / styrene copolymer.
Resin composition for laser direct structuring.
<2> The resin composition for laser direct structuring according to <1>, wherein the phosphorus flame retardant is a condensed phosphate ester.
<3> The resin composition for laser direct structuring according to <1>, wherein the phosphorus flame retardant is a phosphazene compound.
<4> The resin composition for laser direct structuring according to any one of <1> to <3>, wherein the laser direct structuring additive is a spinel structure.
<5> The resin composition for laser direct structuring according to any one of <1> to <4>, wherein the elastomer is a siloxane copolymer elastomer.
<6> 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 of the glass fiber is D2 and the minor axis is D1 is 1.5 or less. The resin composition for laser direct structuring according to any one of <1> to <5>.
<7> 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 of the glass fiber is D2 and the minor axis is D1 exceeds 1.5. The resin composition for laser direct structuring according to any one of <1> to <6>, which is 0 or less.
<8> The resin composition for laser direct structuring according to any one of <1> to <7>, wherein the composition does not substantially contain an acrylonitrile / butadiene / styrene copolymer.
<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>, further having a plating layer on the surface.
<11> The resin molded product according to <9> or <10>, which is a portable electronic device part.
<12> The resin molded product according to <10> or <11>, wherein the plated layer has performance as an antenna.
<13> 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.
<14> The method for producing a resin-molded article with a plating layer according to <13>, wherein the plating is copper plating.
<15> 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 <13> or <14>.
　本発明により、メッキ性を維持しつつ、曲げ弾性率、曲げ強度、シャルピー衝撃強さや荷重たわみ温度などの各種機械的特性および難燃性に優れた樹脂組成物を提供することが可能になった。 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. .
樹脂成形品の表面にメッキを設ける工程を示す概略図である。図１中、１は樹脂成形品を、２はレーザーを、３はレーザーが照射された部分を、４はメッキ液を、５はメッキ層をそれぞれ示している。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.
　以下において、本発明の内容について詳細に説明する。なお、本願明細書において「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。また、本明細書中において、“（メタ）アクリレート”はアクリレートおよびメタクリレートを表し、“（メタ）アクリル”はアクリルおよびメタクリルを表す。 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.
　本発明の樹脂組成物は、ポリカーボネート樹脂４０～９５質量％およびガラス繊維５～６０質量％を含む成分１００質量部に対し、エラストマー０．５～１０質量部、銅およびクロムを含むレーザーダイレクトストラクチャリング添加剤５～２０質量部、リン系難燃剤５～３０質量部、ならびに、ポリテトラフルオロエチレン０．１～１質量部を含み、前記エラストマーは、アクリロニトリル／ブタジエン／スチレン共重合体の含有量が全体の１０質量％未満であり、アクリロニトリル／ブタジエン／スチレン共重合体の含有量は、ポリカーボネート樹脂とアクリロニトリル／ブタジエン／スチレン共重合体の合計量の１０質量％未満であることを特徴とする。 The resin composition of the present invention is a laser direct structuring containing 0.5 to 10 parts by mass of an elastomer, copper and chromium with respect to 100 parts by mass of a component containing 40 to 95% by mass of a polycarbonate resin and 5 to 60% by mass of glass fiber. The elastomer contains 5 to 20 parts by mass of an additive, 5 to 30 parts by mass of a phosphorus-based flame retardant, and 0.1 to 1 part by mass of polytetrafluoroethylene, and the elastomer has a content of acrylonitrile / butadiene / styrene copolymer. The total content of the acrylonitrile / butadiene / styrene copolymer is less than 10% by mass, and the content of the acrylonitrile / butadiene / styrene copolymer is less than 10% by mass of the total amount of the polycarbonate resin and the acrylonitrile / butadiene / styrene copolymer.
　以下、本発明の樹脂組成物の詳細について説明する。
＜ポリカーボネート樹脂＞
　本発明で用いるポリカーボネート樹脂としては特に制限されず、芳香族ポリカーボネート、脂肪族ポリカーボネート、芳香族－脂肪族ポリカーボネートのいずれも用いることができる。中でも芳香族ポリカーボネートが好ましく、さらに、芳香族ジヒドロキシ化合物をホスゲンまたは炭酸のジエステルと反応させることによって得られる熱可塑性芳香族ポリカーボネート重合体または共重合体がより好ましい。 Hereinafter, details of the resin composition of the present invention will be described.
<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.
　該芳香族ジヒドロキシ化合物としては、２，２－ビス（４－ヒドロキシフェニル）プロパン（＝ビスフェノールＡ）、テトラメチルビスフェノールＡ、ビス（４－ヒドロキシフェニル）－Ｐ－ジイソプロピルベンゼン、ハイドロキノン、レゾルシノール、４，４－ジヒドロキシジフェニルなどが挙げられ、好ましくはビスフェノールＡが挙げられる。さらに、難燃性が高い組成物を調製する目的で、上記の芳香族ジヒドロキシ化合物にスルホン酸テトラアルキルホスホニウムが１個以上結合した化合物、またはシロキサン構造を有する両末端フェノール性ＯＨ基含有のポリマーもしくはオリゴマー等を、使用することができる。 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 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.
　本発明で用いるポリカーボネート樹脂の好ましい例には、２，２－ビス（４－ヒドロキシフェニル）プロパンから誘導されるポリカーボネート樹脂；２，２－ビス（４－ヒドロキシフェニル）プロパンと他の芳香族ジヒドロキシ化合物とから誘導されるポリカーボネート共重合体；が含まれる。 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
　ポリカーボネート樹脂の分子量は、溶媒としてメチレンクロライドを用い、温度２５℃で測定された溶液粘度より換算した粘度平均分子量で、１４，０００～３０，０００であるのが好ましく、１５，０００～２８，０００であるのがより好ましく、１６，０００～２６，０００であるのがさらに好ましい。粘度平均分子量が前記範囲であると、機械的強度がより良好となり、且つ成形性もより良好となるので好ましい。 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.
　ポリカーボネート樹脂の製造方法については、特に限定されるものではなく、本発明には、ホスゲン法（界面重合法）、および溶融法（エステル交換法）等の、いずれの方法で製造したポリカーボネート樹脂も使用することができる。また、本発明には、一般的な溶融法の製造工程を経た後に、末端基のＯＨ基量を調整する工程を経て製造されたポリカーボネート樹脂を使用してもよい。 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, you may use the polycarbonate resin manufactured through the process of adjusting the amount of OH groups of a terminal group, after passing through the manufacturing process of a general melting method in this invention.
　さらに、本発明で用いるポリカーボネート樹脂は、バージン原料としてのポリカーボネート樹脂のみならず、使用済みの製品から再生されたポリカーボネート樹脂、いわゆるマテリアルリサイクルされたポリカーボネート樹脂であってもよい。 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.
　その他、本発明で用いるポリカーボネート樹脂については、例えば、特開２０１２－０７２３３８号公報の段落番号００１８～００６６の記載を参酌でき、その内容は本願明細書に組み込まれる。 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.
　本発明の樹脂組成物は、ポリカーボネート樹脂を１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。
　本発明の樹脂組成物において、全樹脂成分中、ポリカーボネート樹脂の割合が、８０質量％以上であることが好ましく、９０質量％以上であることがより好ましく、９５質量％以上であることがさらに好ましい。 The resin composition of the present invention may contain only one type of polycarbonate resin, or may contain two or more types.
In the resin composition of the present invention, the proportion of the polycarbonate resin in all resin components is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more. .
　本発明の樹脂組成物は、ポリカーボネート樹脂の他に、例えばポリアミド樹脂、ポリエステル樹脂、スチレン系樹脂などを含んでいてもよい。しかしながら、これらの樹脂の配合量は、樹脂成分の１０質量％未満であることが好ましく、５質量％以下であることがより好ましく、３質量％以下であることがさらに好ましい。
　本発明の樹脂組成物は、特に、アクリロニトリル／ブタジエン／スチレン共重合体（ＡＢＳ樹脂）の配合量が、ポリカーボネート樹脂とアクリロニトリル／ブタジエン／スチレン共重合体の合計量の１０質量％未満であることが好ましく、５質量％以下であることがより好ましく、３質量％以下であることがさらに好ましく、１質量％以下であることが特に好ましく、実質的に含まないことが最も好ましい。実質的に含まないとは、例えば、積極的に配合されていないことをいう。従って、不純物まで排除するものではない。ここでいうＡＢＳ樹脂には、例えば、後述するエラストマー等に含まれうるＡＢＳ樹脂も含む趣旨である。 The resin composition of the present invention may contain, for example, a polyamide resin, a polyester resin, a styrene resin, etc. in addition to the polycarbonate resin. However, the blending amount of these resins is preferably less than 10% by mass of the resin component, more preferably 5% by mass or less, and further preferably 3% by mass or less.
In the resin composition of the present invention, in particular, the blending amount of acrylonitrile / butadiene / styrene copolymer (ABS resin) is less than 10 mass% of the total amount of the polycarbonate resin and acrylonitrile / butadiene / styrene copolymer. Preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less, It is especially preferable that it is 1 mass% or less, It is most preferable not to contain substantially. “Substantially free” means, for example, that it is not actively blended. Therefore, impurities are not excluded. The ABS resin here includes, for example, an ABS resin that can be contained in an elastomer or the like to be described later.
＜ガラス繊維＞
　本発明の樹脂組成物は、ガラス繊維を含む。
　ガラス繊維は、Ａガラス、Ｃガラス、Ｅガラスなどのガラス組成からなり、特に、Ｅガラス（無アルカリガラス）が好ましい。
　ガラス繊維とは、長さ方向に直角に切断した断面形状が真円状、多角形状で繊維状外嵌を呈するものをいう。
　ガラス繊維の形態は、単繊維や複数本撚り合わせたものを連続的に巻き取った「ガラスロービング」、長さ１～１０ｍｍに切りそろえた「チョップドストランド」、長さ１０～５００μｍ程度に粉砕した「ミルドファイバー」などのいずれであってもよい。かかるガラス繊維としては、旭ファイバーグラス社より、「グラスロンチョップドストランド」や「グラスロンミルドファイバー」の商品名で市販されており、容易に入手可能である。ガラス繊維は、形態が異なるものを併用することもできる。 <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.
　また、本発明ではガラス繊維として、円形断面形状のものおよび異形断面形状のもののいずれも好ましい。ここで、断面形状は、繊維の長さ方向に直角な断面の長径をＤ２、短径をＤ１とするときの長径／短径比（Ｄ２／Ｄ１）で示される扁平率で区別される。本発明における扁平率は、平均扁平率とする。
　本発明では、低そり性の観点から、扁平率１．５を超え８以下のガラス繊維が好ましく、扁平率２～６のガラス繊維がより好ましく、扁平率２～４のガラス繊維がさらに好ましい。かかる扁平ガラスについては、特開２０１１－１９５８２０号公報の段落番号００６５～００７２の記載を参酌でき、この内容は本願明細書に組み込まれる。
　一方、ウェルド強度の向上という観点から、扁平率１．５以下のガラス繊維が好ましく、扁平率１．３以下のガラス繊維がより好ましく、扁平率１．１以下のガラス繊維がさらに好ましく、扁平率１のガラス繊維が特に好ましい。 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 8 or less are preferable, glass fibers having a flatness ratio of 2 to 6 are more preferable, and glass fibers having a flatness ratio of 2 to 4 are more preferable. 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.
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.
　ガラス繊維は、例えば、γ－メタクリルオキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン等のシランカップリング剤等で表面処理されていてもよく、その付着量は、通常、ガラス繊維の質量の０．０１～１質量％である。さらに必要に応じて、脂肪酸アミド化合物、シリコーンオイル等の潤滑剤、第４級アンモニウンム塩等の帯電防止剤、エポキシ樹脂、ウレタン樹脂等の被膜形成能を有する樹脂、被膜形成能を有する樹脂と熱安定剤、難燃剤等の混合物で表面処理されたものを用いることもできる。 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.
　本発明の樹脂組成物におけるガラス繊維の配合量は、ポリマーボネート樹脂とガラス繊維の合計量を１００質量％としたとき、５質量％以上であり、８質量％以上が好ましく、１０質量％以上がより好ましく、また、６０質量％以下であり、５５質量％以下がより好ましく、４０質量％以下がさらに好ましく、３０質量％以下が特に好ましい。
　本発明の樹脂組成物は、ガラス繊維を１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、合計量が上記範囲となる。
　本発明の樹脂組成物では、通常、樹脂成分とガラス繊維で、全成分の７０質量％以上を占めることが好ましい。 The compounding amount of the glass fiber in the resin composition of the present invention is 5% by mass or more, preferably 8% by mass or more, preferably 10% by mass or more when the total amount of the polymer bonate resin and the glass fiber is 100% by mass. More preferably, it is 60% by mass or less, more preferably 55% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less.
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.
＜エラストマー＞
　本発明の樹脂組成物は、エラストマーを含む。エラストマーを含有することで、樹脂組成物の耐衝撃性を改良することができる。本発明に用いるエラストマーとしては、メタクリル酸メチル－ブタジエン－スチレン共重合体（ＭＢＳ樹脂）、ＳＢＳ、ＳＥＢＳと呼ばれているスチレン－ブタジエン系トリブロック共重合体とその水添物、ＳＰＳ、ＳＥＰＳと呼ばれているスチレン－イソプレン系トリブロック共重合体とその水添物、ＴＰＯと呼ばれているオレフィン系熱可塑性エラストマー、ポリエステル系エラストマー、シロキサン系ゴム、アクリレート系ゴム、シロキサン共重合体エラストマー等が挙げられる。エラストマーとしては、特開２０１２－２５１０６１号公報の段落番号００７５～００８８に記載のエラストマー、特開２０１２－１７７０４７号公報の段落番号０１０１～０１０７に記載のエラストマー等を用いることができ、これらの内容は本願明細書に組み込まれる。本発明で特に好ましくは、ＭＢＳ樹脂またはシロキサン共重合エラストマーが用いられ、シロキサン共重合体エラストマーがより好ましい。
　本発明で用いるエラストマーは、アクリロニトリル／ブタジエン／スチレン共重合体の含有量が全体の１０質量％未満であり、５質量％以下であることが好ましく、３質量％以下であることがさらに好ましい。 <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), styrene-butadiene triblock copolymer called SBS, SEBS, and hydrogenated products thereof, SPS, SEPS, Styrene-isoprene triblock copolymer and its hydrogenated product, olefinic thermoplastic elastomer called TPO, polyester elastomer, siloxane rubber, acrylate rubber, siloxane copolymer elastomer, etc. Can be mentioned. 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, an MBS resin or a siloxane copolymer elastomer is particularly preferably used, and a siloxane copolymer elastomer is more preferable.
The elastomer used in the present invention has an acrylonitrile / butadiene / styrene copolymer content of less than 10% by mass, preferably 5% by mass or less, and more preferably 3% by mass or less.
（シロキサン共重合エラストマー）
　本発明で用いるシロキサン共重合エラストマーとしては、ポリオルガノシロキサンとポリアルキル（メタ）アクリレートとを含むシリコーン－アクリル複合ゴムが好ましく、必要に応じて１種以上のビニル系化合物単量体から構成されるビニル系重合体をグラフトさせたグラフト共重合体であってもよい。 (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.
　その基本的な重合体構造としては、ガラス転移温度の低い架橋成分であるポリオルガノシロキサンとポリアルキル（メタ）アクリレートとが相互に絡み合った構造から成る内核層と、１種以上のビニル系化合物単量体から構成されるビニル系重合体からなる外殻層とを有する多層構造重合体である。外殻層を構成するビニル系重合体は、樹脂組成物のマトリックス成分との接着性を改善する効果を有する。このようなグラフト共重合体は、例えば、特開２００４－３５９８８９号公報に開示された方法で製造することができる。 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.
　シリコーン－アクリル複合ゴムの製造に用いるポリオルガノシロキサンは、特に限定されないが、例えば、ジメチルシロキサン単位を構成単位として含有する重合体が好ましい。ポリオルガノシロキサンを構成するジメチルシロキサンとしては、３員環以上のジメチルシロキサン系環状体が挙げられ、３～７員環のものが好ましい。具体的には、ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン等が挙げられる。これらは単独でまたは２種以上を混合して用いられる。これらの中でも、粒子径分布の制御しやすさから、主成分がオクタメチルシクロテトラシロキサンであることが好ましい。 The polyorganosiloxane used for the production of the silicone-acrylic composite rubber is not particularly limited, but for example, a polymer containing dimethylsiloxane units as constituent units 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.
　ポリオルガノシロキサンとしては、ビニル重合性官能基を含有するシロキサンを構成成分として含有していてもよく、また、シロキサン系架橋剤によって架橋されていてもよい。また、ポリオルガノシロキサンの製造方法やグラフト共重合体の製造方法についても特に制限はない。これらは、特開２０１２－１３１９３４号公報段落［００５５］～［００８０］の記載を参酌でき、その内容は本願明細書に組み込まれる。 The polyorganosiloxane may contain a siloxane containing a vinyl polymerizable functional group as a constituent component, and 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. The description in paragraphs [0055] to [0080] of JP 2012-131934 A can be referred to, and the contents thereof are incorporated in the present specification.
　ポリオルガノシロキサンの数平均粒子径は、１０ｎｍ以上であることが好ましく、５０ｎｍ～５μｍであることがより好ましく、１００ｎｍ～３μｍであることがさらに好ましい。ポリオルガノシロキサンの数平均粒子径を１０ｎｍ以上とすることにより、シリコーン－アクリル複合ゴム中のポリアルキル（メタ）アクリレート量が多くなりすぎず、耐衝撃性の低下を抑制することができる。 The number average particle diameter of the polyorganosiloxane is preferably 10 nm or more, more preferably 50 nm to 5 μm, and even more 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 is not excessively increased, and the reduction in impact resistance can be suppressed.
　シリコーン－アクリル複合ゴムの製造に用いるポリアルキル（メタ）アクリレートとは、アルキル（メタ）アクリレート単位を含有する重合体である。
　アルキル（メタ）アクリレートとしては、例えば、メチルアクリレート、エチルアクリレート、ｎ－プロピルアクリレート、ｎ－ブチルアクリレート、２－エチルヘキシルアクリレート等のアルキルアクリレート、及び、メチルメタクリレート、ヘキシルメタクリレート、２－エチルヘキシルメタクリレート、ｎ－ラウリルメタクリレート等のアルキルメタクリレートが挙げられる。これらは１種を単独で、または２種以上併用して用いることができる。 The polyalkyl (meth) acrylate used in the production of the silicone-acrylic composite rubber is a polymer containing alkyl (meth) acrylate units.
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.
　また、ポリアルキル（メタ）アクリレートは、多官能性単量体単位を構成成分として含有する共重合体であってもよい。多官能性単量体としては、例えば、アリルメタクリレート、エチレングリコールジメタクリレート、プロピレングリコールジメタクリレート、１,３－ブチレングリコールジメタクリレート、１,４－ブチレングリコールジメタクリレート、トリアリルシアヌレート、トリアリルイソシアヌレート等が挙げられる。これらは１種を単独で、または２種以上併用して用いることができる。 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 isocyanate. Examples include nurate. These can be used alone or in combination of two or more.
　多官能性単量体を使用する場合の含有量には特に制限はないが、ポリアルキル（メタ）アクリレート１００質量％中の０．１～２質量％であることが好ましく、０．３～１質量％であることがより好ましい。多官能性単量体の含有量を０．１質量％以上とすることにより、複合ゴムのモルフォロジーの変化による衝撃強度の低下を抑制できる傾向にあり、また、多官能性単量体の含有量を２質量％以下とすることにより、衝撃強度がより向上する傾向にある。 The content in the case of using a polyfunctional monomer is not particularly limited, but it is preferably 0.1 to 2% by mass in 100% by mass of polyalkyl (meth) acrylate, and 0.3 to 1 More preferably, it is mass%. By setting the content of the polyfunctional monomer to 0.1% by mass 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 mass or less, the impact strength tends to be further improved.
　本発明おいて、シロキサン共重合エラストマーとしては、ポリオルガノシロキサン－ポリアルキル（メタ）アクリレート複合ゴムに、メタクリル酸アルキル重合体をグラフト重合させたグラフト重合体、ポリオルガノシロキサン－ポリアルキル（メタ）アクリレート複合ゴムに、アクリロニトリル－スチレン共重合体をグラフト重合させたグラフト共重合体が好ましく、これらは、三菱レイヨン社から「メタブレンＳシリーズ」として上市されており、例えば「Ｓ－２０３０」などを使用することが好ましい。 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 “Methbrene S series” by Mitsubishi Rayon Co., for example, “S-2030” or the like is used. It is preferable.
　エラストマーの配合量は、ポリカーボネート樹脂およびガラス繊維を含む成分１００質量部に対し、０．５～１０質量部であり、１～８質量部が好ましく、２～６質量部がより好ましい。
　本発明の樹脂組成物は、エラストマーを１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、合計量が上記範囲となる。 The blending amount of the elastomer is 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, and more preferably 2 to 6 parts by weight with respect to 100 parts by weight of the component including the polycarbonate resin 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.
＜レーザーダイレクトストラクチャリング添加剤（ＬＤＳ添加剤）＞
　本発明の樹脂組成物は、銅およびクロムを含むＬＤＳ添加剤を含む。銅およびクロムを含むＬＤＳ添加剤を用いることで、難燃性およびメッキ性を向上させることができる。
　本発明におけるＬＤＳ添加剤は、ポリカーボネート樹脂（三菱エンジニアリングプラスチックス社製、ユーピロン（登録商標）、Ｓ－３０００Ｆ）１００質量部に対し、ＬＤＳ添加剤と考えられる添加剤を４質量部添加し、１０６４ｎｍのＹＡＧレーザーを用い、出力２．６～１３Ｗの範囲のいずれか、速度１～２ｍ／ｓのいずれか、周波数１０～５０μｓの範囲のいずれかの条件でレーザー照射により印字し、続いて、試験片を硫酸にて脱脂後、キザイ社製ＴＨＰアルカリアクチ及びＴＨＰアルカリアクセで処理後、キザイ社製ＳＥＬカッパ―にてメッキ処理を適用したときに、メッキを形成できる化合物をいう。本発明で用いるＬＤＳ添加剤は、合成品であってもよいし、市販品を用いてもよい。また、市販品はＬＤＳ添加剤として市販されているものの他、本発明におけるＬＤＳ添加剤の要件を満たす限り、他の用途として販売されている物質であってもよい。 <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.
　本発明におけるＬＤＳ添加剤は、銅およびクロムを含んでいれば特に限定されない。本発明におけるＬＤＳ添加剤としては、銅を１０～３０質量％含むことが好ましい。また、クロムを１５～５０質量％含むことが好ましい。
　本発明におけるＬＤＳ添加剤は、銅およびクロムを含む酸化物であることが好ましい。 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.
　銅およびクロムの含有形態としては、スピネル構造が好ましい。スピネル構造とは、複酸化物でＡＢ2Ｏ4型の化合物（ＡとＢは金属元素）にみられる代表的結晶構造型の一つである。 As the copper and chromium content, a spinel structure is preferable. The 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).
　ＬＤＳ添加剤は、銅およびクロムの他に、他の金属を微量含んでいてもよい。他の金属としては、アンチモン、スズ、鉛、インジウム、鉄、コバルト、ニッケル、亜鉛、カドミウム、銀、ビスマス、ヒ素、マンガン、マグネシウム、カルシウムなどが例示され、マンガンが好ましい。これら金属は酸化物として存在していてもよい。
 本発明の好ましい実施形態の一例は、銅クロム酸化物以外の金属酸化物の含有量が１０質量％以下であるＬＤＳ添加剤である。 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, and manganese is preferable. These metals may exist as oxides.
An example of a preferred embodiment of the present invention is an LDS additive in which the content of metal oxides other than copper chromium oxide is 10% by mass or less.
　ＬＤＳ添加剤の粒子径は、０．０１～５０μｍであることが好ましく、０．０５～３０μｍであることがより好ましい。このような構成とすることにより、メッキを適応した際のメッキ表面状態の均一性が良好になる傾向にある。 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.
　ＬＤＳ添加剤の配合量は、ポリカーボネート樹脂およびガラス繊維を含む成分１００質量部に対し、５～２０質量部であり、６～１５質量部が好ましく、８～１３質量部がより好ましい。配合量が２０質量部以上配合すると、衝撃性が低下したり、ポリカーボネート樹脂が分解したり、難燃性が劣ってしまう。
　本発明の樹脂組成物は、ＬＤＳ添加剤を１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、合計量が上記範囲となる。 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 polycarbonate resin and the glass fiber. When the blending amount is 20 parts by mass or more, the impact property is lowered, the polycarbonate resin 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.
＜リン系難燃剤＞
　本発明の組成物は、リン系難燃剤を含む。リン系難燃剤は、縮合リン酸エステル化合物および／またはホスファゼン化合物が好ましい。
　リン系難燃剤の配合量は、ポリカーボネート樹脂およびガラス繊維を含む成分１００質量部に対し、５～３０質量部であり、８～２５質量部が好ましく、１０～２０質量部が特に好ましい。
　本発明の樹脂組成物は、リン系難燃剤を、１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、合計量が上記範囲となる。 <Phosphorus flame retardant>
The composition of the present invention contains a phosphorus-based flame retardant. The phosphorus-based flame retardant is preferably a condensed phosphate ester compound and / or a phosphazene compound.
The compounding amount of the phosphorus-based flame retardant is 5 to 30 parts by mass, preferably 8 to 25 parts by mass, and particularly preferably 10 to 20 parts by mass with respect to 100 parts by mass of the component including the polycarbonate resin and the glass fiber.
The resin composition of the present invention may contain only one type of phosphorus-based flame retardant, or may contain two or more types. When two or more types are included, the total amount falls within the above range.
＜＜縮合リン酸エステル＞＞
　本発明の樹脂組成物は、縮合リン酸エステルを配合させることで、難燃性を向上させることができる。
　縮合リン酸エステルとしては、下記の一般式（１）で表されるものであるのが好ましい。 << Condensed phosphate ester >>
The resin composition of this invention can improve a flame retardance by mix | blending condensed phosphate ester.
The condensed phosphate ester is preferably represented by the following general formula (1).
一般式（１）
Figure JPOXMLDOC01-appb-C000001
 （式中、Ｒ1、Ｒ2、Ｒ3およびＲ4は、それぞれ独立して水素原子または有機基を表す。ただし、Ｒ1、Ｒ2、Ｒ3およびＲ4が全て水素原子の場合を除く。Ｘは２価の有機基を表し、ｐは０または１であり、ｑは１以上の整数、ｒは０または１以上の整数を表す。） General formula (1)
Figure JPOXMLDOC01-appb-C000001
 (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.)
　上記の一般式（１）において、有機基とは、例えば、置換基を有する、または有しないアルキル基、シクロアルキル基、アリール基が挙げられ、該置換基は、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、ハロゲン原子、ハロゲン化アリール基等が挙げられる。またこれらの置換基を組み合わせた基、あるいはこれらの置換基を酸素原子、イオウ原子、窒素原子などにより結合して組み合わせた基などでもよい。また２価の有機基とは、上記の有機基から炭素原子１個を除いてできる２価以上の基をいう。例えば、アルキレン基、フェニレン基、置換フェニレン基、ビスフェノール類から誘導されるような多核フェニレン基などが挙げられる。 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.
　上記の一般式（１）で示される縮合リン酸エステルの具体例としては、例えば、トリメチルフォスフェート、トリエチルフォスフェート、トリブチルフォスフェート、トリオクチルフォスフェート、トリフェニルフォスフェート、トリクレジルフォスフェート、トリクレジルフェニルフォスフェート、オクチルジフェニルフォスフェート、ジイソプロピルフェニルフォスフェート、トリス（クロルエチル）フォスフェート、トリス（ジクロルプロピル）フォスフェート、トリス（クロルプロピル）フォスフェート、ビス（２，３－ジブロモプロピル）フォスフェート、ビス（２，３－ジブロモプロピル）－２，３－ジクロルフォスフェート、ビス（クロルプロピル）モノオクチルフォスフェート、ビスフェノールＡテトラフェニルフォスフェート、ビスフェノールＡテトラクレジルジフォスフェート、ビスフェノールＡテトラキシリルジフォスフェート、ヒドロキノンテトラフェニルジフォスフェート、ヒドロキノンテトラクレジルフォスフェート、ヒドロキノンテトラキシリルジフォスフェート等の種々のものが例示される。
　また、市販の縮合リン酸エステルとしては、例えば、大八化学工業（株）より「ＣＲ７３３Ｓ」（レゾルシノールビス（ジフェニルホスフェート））、「ＣＲ７４１」（ビスフェノールＡビス（ジフェニルホスフェート））、「ＰＸ－２００」（レゾルシノールビス（ジキシレニルホスフェート））、旭電化工業（株）より「アデカスタブＦＰ－７００」（２，２－ビス（ｐ－ヒドロキシフェニル）プロパン・トリクロロホスフィンオキシド重縮合物（重合度１～３）のフェノール縮合物）といった商品名で販売されており、容易に入手可能である。 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 (degree of polymerization 1 to It is sold under the trade name such as 3) phenol condensate and is readily available.
＜＜ホスファゼン化合物＞＞
　本発明の樹脂組成物は、ホスファゼン化合物を配合させることで、難燃性を向上させることができる。
　ホスファゼン化合物は、分子中に－Ｐ＝Ｎ－結合を有する有機化合物であり、好ましくは、下記一般式（１）で表される環状ホスファゼン化合物、下記一般式（２）で表される鎖状ホスファゼン化合物、ならびに、下記一般式（１）及び下記一般式（２）からなる群より選択される少なくとも一種のホスファゼン化合物が架橋基によって架橋されてなる架橋ホスファゼン化合物からなる群より選択される少なくとも１種の化合物である。 << Phosphazene Compound >>
The resin composition of this invention can improve a flame retardance by mix | blending a phosphazene compound.
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.
Figure JPOXMLDOC01-appb-C000002
 　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。
Figure JPOXMLDOC01-appb-C000002
 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.
Figure JPOXMLDOC01-appb-C000003
 　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。
Figure JPOXMLDOC01-appb-C000003
 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.
　上記式（１）及び式（２）中、アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ－ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基等が挙げられるが、通常メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ－ブチル基、ペンチル基、ヘキシル基等の炭素数１～６のアルキル基が好ましく、メチル基、エチル基、プロピル基等の炭素数１～４のアルキル基が特に好ましい。 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.
　シクロアルキル基としては、例えば、シクロペンチル基、シクロヘキシル基等の炭素数５～１４のシクロアルキル基が挙げられるが、中でも炭素数５～８のシクロアルキル基が好ましい。 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.
　アルケニル基としては、例えば、ビニル基、アリル基等の炭素数２～８のアルケニル基が挙げられ、シクロアルケニル基としては、例えば、シクロペンチル基、シクロヘキシル基等の炭素数５～１２のシクロアルケニル基が挙げられる。 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.
　アルキニル基としては、例えば、エチニル基、プロピニル基等の炭素数２～８のアルキニル基やエチニルベンゼン基等のアリール等も挙げられる。 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.
　上記アリール基としては、例えば、フェニル基、メチルフェニル（即ち、トリル）基、ジメチルフェニル（即ち、キシリル）基、トリメチルフェニル基、ナフチル基等の炭素数６～２０のアリール基が挙げられるが、なかでも炭素数６～１０のアリール基が好ましく、フェニル基が特に好ましい。 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.
　アルキルアリール基としては、例えば、ベンジル基、フェネチル基、フェニルプロピル基等の炭素数６～２０のアラルキル基が挙げられるが、なかでも炭素数７～１０のアラルキル基が好ましく、ベンジル基が特に好ましい。 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. .
　なかでも、上記一般式（１）におけるＲ1及びＲ2、上記一般式（２）におけるＲ3及びＲ4が、アリール基、アリールアルキル基であるものが好ましい。このような芳香族ホスファゼンを用いることで、樹脂組成物の熱安定性を効果的に高めることができる。このような観点より、上記Ｒ1、Ｒ2、Ｒ3及びＲ4は、アリール基であることがより好ましく、フェニル基であることが特に好ましい。 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.
　一般式（１）及び（２）で表される環状及び／又は鎖状ホスファゼン化合物としては、例えば、フェノキシホスファゼン、ｏ－トリルオキシホスファゼン、ｍ－トリルオキシホスファゼン、ｐ－トリルオキシホスファゼン等の（ポリ）トリルオキシホスファゼン、ｏ，ｍ－キシリルオキシホスファゼン、ｏ，ｐ－キシリルオキシホスファゼン、ｍ，ｐ－キシリルオキシホスファゼン等の（ポリ）キシリルオキシホスファゼン、ｏ，ｍ，ｐ－トリメチルフェニルオキシホスファゼン、フェノキシｏ－トリルオキシホスファゼン、フェノキシｍ－トリルオキシホスファゼン、フェノキシｐ－トリルオキシホスファゼン等の（ポリ）フェノキシトリルオキシホスファゼン、フェノキシｏ，ｍ－キシリルオキシホスファゼン、フェノキシｏ，ｐ－キシリルオキシホスファゼン、フェノキシｍ，ｐ－キシリルオキシホスファゼン等（ポリ）フェノキシトリルオキシキシリルオキシホスファゼン、フェノキシｏ，ｍ，ｐ－トリメチルフェニルオキシホスファゼン等が例示でき、好ましくは環状及び／又は鎖状フェノキシホスファゼン等である。 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.
　一般式（１）で表される環状ホスファゼン化合物としては、Ｒ1及びＲ2がフェニル基である環状フェノキシホスファゼンが特に好ましい。このような環状フェノキシホスファゼン化合物としては、例えば、塩化アンモニウムと五塩化リンとを１２０～１３０℃の温度で反応させて得られる環状及び直鎖状のクロロホスファゼン混合物から、ヘキサクロロシクロトリホスファゼン、オクタクロロシクロテトラホスファゼン、デカクロロシクロペンタホスファゼン等の環状のクロルホスファゼンを取り出した後にフェノキシ基で置換して得られる、フェノキシシクロトリホスファゼン、オクタフェノキシシクロテトラホスファゼン、デカフェノキシシクロペンタホスファゼン等の化合物が挙げられる。また、該環状フェノキシホスファゼン化合物は、一般式（１）中のａが３～８の整数である化合物が好ましく、ａの異なる化合物の混合物であってもよい。 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. . Further, 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.
　上記ａの平均は、３～５であることが好ましく、３～４であることがより好ましい。また、なかでも、ａ＝３のものが５０質量％以上、ａ＝４のものが１０～４０質量％、ａ＝５以上のものが合わせて３０質量％以下である化合物の混合物が好ましい。 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.
　一般式（２）で表される鎖状ホスファゼン化合物としては、Ｒ3及びＲ4がフェニル基である鎖状フェノキシホスファゼンが特に好ましい。このような鎖状フェノキシホスファゼン化合物は、例えば、上記の方法で得られるヘキサクロロシクロトリホスファゼンを２２０～２５０℃の温度で開還重合し、得られた重合度３～１００００の直鎖状ジクロロホスファゼンをフェノキシ基で置換することにより得られる化合物が挙げられる。該直鎖状フェノキシホスファゼン化合物の、一般式（２）中のｂは、好ましくは３～１０００、より好ましくは３～１００、さらに好ましくは３～２５である。 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.
　架橋ホスファゼン化合物としては、例えば、４，４'－スルホニルジフェニレン（すなわち、ビスフェノールＳ残基）の架橋構造を有する化合物、２，２－（４，４'－ジフェニレン）イソプロピリデン基の架橋構造を有する化合物、４，４'－オキシジフェニレン基の架橋構造を有する化合物、４，４'－チオジフェニレン基の架橋構造を有する化合物等の、４，４'－ジフェニレン基の架橋構造を有する化合物等が挙げられる。 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.
　また、架橋ホスファゼン化合物としては、一般式（１）においてＲ1、Ｒ2がフェニル基である環状フェノキシホスファゼン化合物が上記架橋基によって架橋されてなる架橋フェノキシホスファゼン化合物、又は、上記一般式（２）においてＲ3、Ｒ4がフェニル基である鎖状フェノキシホスファゼン化合物が上記架橋基によって架橋されてなる架橋フェノキシホスファゼン化合物が難燃性の点から好ましく、環状フェノキシホスファゼン化合物が上記架橋基によって架橋されてなる架橋フェノキシホスファゼン化合物がより好ましい。
　また、架橋フェノキシホスファゼン化合物中のフェニレン基の含有量は、一般式（１）で表される環状ホスファゼン化合物及び／又は一般式（２）で表される鎖状フェノキシホスファゼン化合物中の全フェニル基及びフェニレン基数を基準として、通常５０～９９．９％、好ましくは７０～９０％である。また、該架橋フェノキシホスファゼン化合物は、その分子内にフリーの水酸基を有しない化合物であることが特に好ましい。 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.
　本発明においては、ホスファゼン化合物は、上記一般式（１）で表される環状フェノキシホスファゼン化合物、及び、上記一般式（１）で表される環状フェノキシホスファゼン化合物が架橋基によって架橋されてなる架橋フェノキシホスファゼン化合物よる成る群から選択される少なくとも１種であることが、樹脂組成物の難燃性及び機械的特性の点から好ましい。 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.
＜ポリテトラフルオロエチレン＞
　本発明の樹脂組成物は、ポリテトラフルオロエチレン（ＰＴＦＥ）を含有する。ポリテトラフルオロエチレンとしては、フィブリル形成能を有するポリテトラフルオロエチレンが好ましい。フィブリル形成能を有するポリテトラフルオロエチレンはＡＳＴＭ規格でタイプ３に分類される。フィブリル形成能を有するポリテトラフルオロエチレンとしては、例えば三井・デュポンフロロケミカル（株）製のテフロン（登録商標）６－Ｊや、ダイキン化学工業（株）製のポリフロンＦ２０１Ｌ、ＦＡ５００Ｂ、ＦＡ５００Ｃが挙げられる。また、ポリテトラフルオロエチレンの水性分散液として、ダイキン化学工業（株）製のフルオンＤ－１や、ビニル系単量体を重合してなる多層構造を有するポリテトラフルオロエチレン化合物が挙げられる。いずれのタイプも本発明の樹脂組成物に用いることができる。 <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.
　ポリテトラフルオロエチレンを含有した樹脂組成物を射出成形した成形品の外観をより向上させるためには、有機系重合体で被覆された特定の被覆ポリテトラフルオロエチレン（以下、被覆ポリテトラフルオロエチレンと略記することがある）を使用することができる。特定の被覆ポリテトラフルオロエチレンとは、被覆ポリテトラフルオロエチレン中のポリテトラフルオロエチレンの含有比率が４０～９５質量％の範囲内となるものであり、中でも、４３～８０質量％、更には４５～７０質量％、特には４７～６０質量％となるものが好ましい。特定の被覆ポリテトラフルオロエチレンとしては、例えば三菱レイヨン社製のメタブレンＡ－３８００、Ａ－３７００、ＫＡ－５５０３や、ＰＩＣ社製のＰｏｌｙ ＴＳ ＡＤ００１等が使用できる。 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.
　ポリテトラフルオロエチレンの配合量は、ポリカーボネート樹脂およびガラス繊維を含む成分１００質量部に対し、０．１～１質量部であり、０．２～０．８質量部がより好ましく、０．３～０．６質量部が特に好ましい。なお、被覆ポリテトラフルオロエチレンの場合、添加量はポリテトラフルオロエチレン純分の量に相当する。ポリテトラフルオロエチレンの配合量が０．１質量部未満の場合には、難燃効果としては不十分であり、一方、１質量部を超えると成形品外観の低下が起こる場合がある。
　本発明の樹脂組成物は、ポリテトラフルオロエチレンを１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、合計量が上記範囲となる。 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 polycarbonate resin 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.
＜有機リン系安定剤＞
　本発明の樹脂組成物は、有機リン系安定剤を含むことが好ましい。有機リン系安定剤を配合することで、ＬＤＳ添加剤によるポリカーボネート樹脂を分解しにくくし、本発明の効果がより効果的に発揮される。有機リン系安定剤としては、特開２００９－３５６９１号公報の段落番号００７３～００９５の記載を参酌でき、これらの内容は本願明細書に組み込まれる。より好ましい有機リン系安定剤としては、下記一般式（３）で表される化合物である。 <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).
一般式（３）
Ｏ＝Ｐ（ＯＨ）m（ＯＲ）3-m・・・（３）
（一般式（３）中、Ｒはアルキル基またはアリール基であり、それぞれ同一であっても異なっていてもよい。ｍは０～２の整数である。）
　Ｒは炭素数１～３０のアルキル基または、炭素数６～３０のアリール基であることが好ましく、炭素数２～２５のアルキル基、フェニル基、ノニルフェニル基、ステアリルフェニル基、２，４－ジｔｅｒｔ－ブチルフェニル基、２，４－ジｔｅｒｔ－ブチルメチルフェニル基、トリル基がより好ましい。 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.
　中でも、下記一般式（３’）で表されるリン酸エステルが好ましい。 Of these, phosphate esters represented by the following general formula (3 ') are preferred.
Ｏ＝Ｐ（ＯＨ）m'（ＯＲ’）3-m'・・・（３’）
　一般式（３’）中、Ｒ’は炭素数２～２５のアルキル基であり、それぞれ同一であっても異なっていてもよい。ｍ’は１または２である。ここで、アルキル基としては、オクチル基、２－エチルヘキシル基、イソオクチル基、ノニル基、イソノニル基、デシル基、イソデシル基、ドデシル基、トリデシル基、イソトリデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基などが挙げられ、テトラデシル基、ヘキサデシル基およびオクタデシル基が好ましく、オクタデシル基が特に好ましい。 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.
　リン酸エステルとしては、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリオクチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリス（ノニルフェニル）ホスフェート、２－エチルフェニルジフェニルホスフェート、テトラキス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）－４，４－ジフェニレンホスフォナイト、モノステアリルアシッドホスフェート、ジステアリルアシッドホスフェート等が挙げられる。 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.
　亜リン酸エステルとしては、下記一般式（４）で表される化合物も好ましい。
一般式（４）
Figure JPOXMLDOC01-appb-C000004
 （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)
Figure JPOXMLDOC01-appb-C000004
 (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.
　亜リン酸エステルとしては、例えば、トリフェニルホスファイト、トリスノニルフェニルホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、トリノニルホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリオクタデシルホスファイト、ジステアリルペンタエリスリトールジホスファイト、トリシクロヘキシルホスファイト、モノブチルジフエニルホスファイト、モノオクチルジフエニルホスファイト、ビス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ペンタエリスリトールホスファイト、ビス（２．６－ジ－ｔｅｒｔ－ブチル－４－メチルフェニル）ペンタエリスリトールホスファイト、２，２－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）オクチルホスファイト等の亜リン酸のトリエステル、ジエステル、モノエステル等が挙げられる。 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.
　本発明の樹脂組成物がリン系安定剤を含む場合、該リン系安定剤の配合量は、ポリカーボネート樹脂およびガラス繊維を含む成分１００質量部に対し、０．０１～５質量が好ましく、０．０５～０．３質量部がより好ましく、０．０８～０．２５質量部がさらに好ましい。０．０１質量部以上とすることで、ＬＤＳ添加剤によるポリカーボネート樹脂の分解をより効果的に抑制させることができ、５質量部以下とすることで、ガラス繊維とポリカーボネートとの密着強度を上げ、強度をより向上させることができる。 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 polycarbonate resin and glass fiber. 05 to 0.3 parts by mass is more preferable, and 0.08 to 0.25 parts by mass is even more 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.
　本発明の樹脂組成物は、リン系安定剤を１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、合計量が上記範囲となることが好ましい。 The resin composition of the present invention may contain only one type of phosphorous stabilizer, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
　本発明では、特に、有機リン系安定剤として、モノステアリルアシッドホスフェートおよび／またはジステアリルアシッドホスフェートを、ポリカーボネート樹脂およびガラス繊維１００質量部に対し、０．０１～０．５質量部配合することが好ましく、０．０５～０．３質量部含むことがより好ましく、０．０８～０．２５質量部含むことが特に好ましい。０．０１質量部以上とすることにより、ポリカーボネート樹脂の分解を顕著に抑制でき、０．５質量部以下とすることにより、ガラス繊維との密着性を向上させ、機械的強度を顕著に向上させることができる。 In the present invention, in particular, 0.01 to 0.5 parts by mass of monostearyl acid phosphate and / or distearyl acid phosphate as an organophosphorus stabilizer is added to 100 parts by mass of the polycarbonate resin and the glass fiber. Preferably, 0.05 to 0.3 parts by mass is included, and 0.08 to 0.25 parts by mass is particularly 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.
＜酸化防止剤＞
　本発明の樹脂組成物は、酸化防止剤を含んでいてもよい。酸化防止剤としては、フェノール系酸化防止剤が好ましく、より具体的には、２，６－ジ－オブチル－４－メチルフェノール、ｎ－オクタデシル－３－（３，５－ジ－ｔ－ブチル－４'－ヒドロキシフェニル）プロピオネート、テトラキス［メチレン－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］メタン、トリス（３，５－ジ－ｔ－ブチル－４―ヒドロキシベンジル）イソシアヌレート、４，４'－ブチリデンビス－（３－メチル－６－ｔ－ブチルフェノール）、トリエチレングリコール－ビス［３－（３－ｔ－ブチル－ヒドロキシ－５－メチルフェニル）プロピオネート］、および３，９－ビス｛２－［３－（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ］－１，１－ジメチルエチル｝－２，４，８，１０－テトラオキサスピロ［５，５］ウンデカン等が挙げられる。中でも、テトラキス［メチレン－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］メタンが好ましい。
　本発明の樹脂組成物が酸化防止剤を含む場合、該酸化防止剤の配合量は、ポリカーボネート樹脂およびガラス繊維を含む成分１００質量部に対し、０．０１～５質量部であることが好ましく、０．０５～３質量部がより好ましい。
　本発明の樹脂組成物は酸化防止剤を１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、合計量が上記範囲となることが好ましい。 <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-butyl-4-methylphenol, n-octadecyl-3- (3,5-di-t-butyl- 4′-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-tert-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 Ethyl} -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 the present invention contains an antioxidant, the 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 polycarbonate resin and 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 is preferably within the above range.
＜離型剤＞
　本発明の樹脂組成物は、離型剤を含んでいてもよい。離型剤は、脂肪族カルボン酸、脂肪族カルボン酸エステル、および数平均分子量２００～１５０００の脂肪族炭化水素化合物から選ばれる少なくとも１種の化合物が好ましい。中でも、脂肪族カルボン酸、および脂肪族カルボン酸エステルから選ばれる少なくとも１種の化合物がより好ましく用いられる。 <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.
　脂肪族カルボン酸としては、飽和または不飽和の脂肪族モノカルボン酸、ジカルボン酸またはトリカルボン酸を挙げることができる。本明細書では、脂肪族カルボン酸の用語は、脂環式カルボン酸も包含する意味で用いる。脂肪族カルボン酸の中でも、炭素数６～３６のモノまたはジカルボン酸が好ましく、炭素数６～３６の脂肪族飽和モノカルボン酸がより好ましい。このような脂肪族カルボン酸の具体例としては、パルミチン酸、ステアリン酸、吉草酸、カプロン酸、カプリン酸、ラウリン酸、アラキン酸、ベヘン酸、リグノセリン酸、セロチン酸、メリシン酸、テトラリアコンタン酸、モンタン酸、グルタル酸、アジピン酸、アゼライン酸等を挙げることができる。 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.
　脂肪族カルボン酸エステルを構成する脂肪族カルボン酸成分としては、前記脂肪族カルボン酸と同じものが使用できる。一方、脂肪族カルボン酸エステルを構成するアルコール成分としては、飽和または不飽和の１価アルコール、飽和または不飽和の多価アルコール等を挙げることができる。これらのアルコールは、フッ素原子、アリール基等の置換基を有していてもよい。これらのアルコールのうち、炭素数３０以下の１価または多価の飽和アルコールが好ましく、さらに炭素数３０以下の脂肪族飽和１価アルコールまたは多価アルコールが好ましい。ここで脂肪族アルコールは、脂環式アルコールも包含する。これらのアルコールの具体例としては、オクタノール、デカノール、ドデカノール、ステアリルアルコール、ベヘニルアルコール、エチレングリコール、ジエチレングリコール、グリセリン、ペンタエリスリトール、２，２－ジヒドロキシペルフルオロプロパノール、ネオペンチレングリコール、ジトリメチロールプロパン、ジペンタエリスリトール等を挙げることができる。これらの脂肪族カルボン酸エステルは、不純物として脂肪族カルボン酸および／またはアルコールを含有していてもよく、複数の化合物の混合物であってもよい。脂肪族カルボン酸エステルの具体例としては、蜜ロウ（ミリシルパルミテートを主成分とする混合物）、ステアリン酸ステアリル、ベヘン酸ベヘニル、ベヘン酸オクチルドデシル、グリセリンモノパルミテート、グリセリンモノステアレート、グリセリンジステアレート、グリセリントリステアレート、ペンタエリスリトールモノパルミテート、ペンタエリスリトールモノステアレート、ペンタエリスリトールジステアレート、ペンタエリスリトールトリステアレート、ペンタエリスリトールテトラステアレートを挙げることができる。 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.
　本発明の樹脂組成物が離型剤を含む場合、該離型剤の配合量は、ポリカーボネート樹脂およびガラス繊維を含む成分１００質量部に対し、０．０１～５質量部であることが好ましく、０．０５～３質量部がより好ましい。
　本発明の樹脂組成物は離型剤を１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、合計量が上記範囲となることが好ましい。 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 a component containing a polycarbonate resin and 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 is preferably within the above range.
　本発明の樹脂組成物は、本発明の趣旨を逸脱しない範囲で、他の成分を含んでいてもよい。他の成分としては、リン系安定剤以外の安定剤、紫外線吸収剤、無機フィラー、蛍光増白剤、帯電防止剤、防曇剤、滑剤、アンチブロッキング剤、流動性改良剤、可塑剤、分散剤、防菌剤などが挙げられる。これらは２種以上を併用してもよい。
　これらの成分については、特開２００７－３１４７６６号公報、特開２００８－１２７４８５号公報および特開２００９－５１９８９号公報、特開２０１２－７２３３８号公報等の記載を参酌でき、これらの内容は本願明細書に組み込まれる。 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.
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.
　本発明のポリカーボネート樹脂組成物の製造方法は、特に定めるものではなく、公知の熱可塑性樹脂組成物の製造方法を広く採用できる。具体的には、各成分を、タンブラーやヘンシェルミキサーなどの各種混合機を用い予め混合した後、バンバリーミキサー、ロール、ブラベンダー、単軸混練押出機、二軸混練押出機、ニーダーなどで溶融混練することによって樹脂組成物を製造することができる。 The method for producing the polycarbonate 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 and 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.
　また、例えば、各成分を予め混合せずに、または、一部の成分のみを予め混合し、フィーダーを用いて押出機に供給して溶融混練して、本発明の樹脂組成物を製造することもできる。
　さらに、例えば、一部の成分を予め混合し押出機に供給して溶融混練することで得られる樹脂組成物をマスターバッチとし、このマスターバッチを再度残りの成分と混合し、溶融混練することによって本発明の樹脂組成物を製造することもできる。 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.
　本発明では、ホスファゼン化合物をマスターバッチとして、また、特定の顆粒状ホスファゼンとして配合することが好ましい。具体的には、以下の態様が例示される。
（第一の態様）
　第一の態様としては、重量平均分子量１５０００～５５０００の芳香族ポリカーボネート樹脂（Ａ）４０～６５質量％と芳香族ホスファゼン化合物（Ｂ）３５～６０質量％とを溶融混練することによって得られることを特徴とする難燃剤マスターバッチであって、（Ａ）成分と（Ｂ）成分の合計が９５～１００質量％であることを特徴とする難燃剤マスターバッチが例示される。このような構成とすることにより、樹脂と溶融混練する際の作業性にも優れ、さらには熱可塑性樹脂に配合した際に、難燃性、機械物性に優れる難燃剤マスターバッチが得られる。
（第二の態様）
　第二の態様としては、重量平均分子量５，０００～５５，０００の芳香族ポリカーボネート樹脂（Ａ）と芳香族ホスファゼン化合物（Ｂ）を加圧ニーダーにて溶融混練して得られる難燃剤マスターバッチである。このような構成とすることにより、難燃性と機械物性を効果的に且つ安定的に発現させることができる難燃剤マスターバッチが得られる。 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 weight 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 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.
（第三の態様）
　第三の態様としては、芳香族ポリカーボネート樹脂（Ａ）８５～２０質量％と芳香族ホスファゼン化合物（Ｂ）１５～８０質量％の合計１００質量部と、フルオロポリマー（Ｃ）を０．００５～２質量部とを溶融混練することによって得られることを特徴とする難燃剤マスターバッチである。この様な構成とすることにより、樹脂と溶融混練する際の作業性にも優れ、さらには熱可塑性樹脂に配合した際に、難燃性、機械物性に優れる難燃剤マスターバッチが得られる。 (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.
（第四の態様）
　第四の態様としては、目開き４００μｍの篩上の割合が５５質量％以上で、嵩密度が０．３～１．５ｇ／ｍｌであることを特徴とする顆粒状ホスファゼン化合物として樹脂に配合する態様である。ホスファゼン化合物は、常温で微粉状であるが、圧縮やせん断に対して固化する性質を有しており、このままでは熱可塑性樹脂と共に押出機にて溶融混練する際、押出機スクリュウへホスファゼン化合物が固着する等の不具合を生じやすいが、顆粒状ホスファゼン化合物とすることにより、押出機スクリュウへの固着等の不具合を起こしにくくできる。 (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.
（第五の態様）
　ホスファゼン化合物（Ａ）に、目開き１０００μｍの篩を通過する割合が３０質量％以上であるポリカーボネート樹脂粉粒体（Ｂ）を、（Ａ）／（Ｂ）の質量比が８５／１５～５／９５で混合してなり、嵩密度が０．４～１．５ｇ／ｍｌであることを特徴とする顆粒状ホスファゼン化合物として樹脂に配合する態様である。このような構成とすることにより、生産性に優れ、熱可塑性樹脂と溶融混練する際の作業性にも優れる。 (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.
　本発明の樹脂組成物から樹脂成形品を製造する方法は、特に限定されるものではなく、熱可塑性樹脂について一般に採用されている成形法、すなわち一般的な射出成形法、超高速射出成形法、射出圧縮成形法、二色成形法、ガスアシストなどの中空成形法、断熱金型を用いた成形法、急速加熱金型を用いた成形法、発泡成形（超臨界流体も含む）、インサ－ト成形、ＩＭＣ（インモ－ルドコ－ティング成形）成形法、押出成形法、シ－ト成形法、熱成形法、回転成形法、積層成形法、プレス成形法等を採用することができる。また、ホットランナ－方式を用いた成形法を選択することもできる。 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.
　次に、本発明の樹脂組成物を成形した樹脂成形品の表面にメッキを設ける工程を図１に従って説明する。図１は、レーザーダイレクトストラクチャリング技術によって、樹脂成形品１の表面にメッキを形成する工程を示す概略図である。図１では、樹脂成形品１は、平坦な基板となっているが、必ずしも平坦な基板である必要はなく、一部または全部が曲面している樹脂成形品であってもよい。また、樹脂成形品は、最終製品に限らず、各種部品も含む趣旨である。本発明における樹脂成形品としては、携帯電子機器部品が好ましい。携帯電子機器部品は、高い耐衝撃特性と剛性、優れた耐熱性を併せ持つうえ、異方性が小さく、反りが小さいという特徴を有し、電子手帳、携帯用コンピューター等のＰＤＡ、ポケットベル、携帯電話、ＰＨＳなどの内部構造物および筐体として極めて有効であり、特に樹脂成形品がリブを除く平均肉厚が１．２ｍｍ以下（下限値は特に定めるものではないが、例えば、０．４ｍｍ以上）である平板形状の携帯電子機器用部品に適しており、中でも筐体として特に適している。 Next, the process of providing plating on the surface of the 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.
　再び図１に戻り、樹脂成形品１にレーザー２を照射する。ここでのレーザーとは、特に定めるものではなく、ＹＡＧレーザー、エキシマレーザー、電磁線等の公知のレーザーから適宜選択することができ、ＹＧＡレーザーが好ましい。また、レーザーの波長も特に定めるものではない。好ましい波長範囲は、２００ｎｍ～１２００ｎｍである。特に好ましくは８００～１２００ｎｍである。
　レーザーが照射されると、レーザーが照射された部分３のみ、樹脂成形品１が活性化される。この活性化された状態で、樹脂成形品１をメッキ液４に適用する。メッキ液４としては、特に定めるものではなく、公知のメッキ液を広く採用することができ、金属成分として銅、ニッケル、金、銀、パラジウムが混合されているものが好ましく、銅がより好ましい。
　樹脂成形品１をメッキ液４に適用する方法についても、特に定めるものではないが、例えば、メッキ液を配合した液中に投入する方法が挙げられる。メッキ液を適用後の樹脂成形品は、レーザー照射した部分のみ、メッキ層５が形成される。
　本発明の方法では、１ｍｍ以下、さらには、１５０μｍ以下の幅の回線間隔（下限値は特に定めるものではないが、例えば、３０μｍ以上）を形成することができる。かかる回路は携帯電子機器部品のアンテナとして好ましく用いられる。すなわち、本発明の樹脂成形品の好ましい実施形態の一例として、携帯電子機器部品の表面に設けられたメッキ層が、アンテナとしての性能を保有する樹脂成形品が挙げられる。 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 YGA 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, it is possible to form a line interval (a lower limit value is not specifically defined, for example, 30 μm or more) having a width of 1 mm or less, and further 150 μm or less. 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 resin molded product in which a plating layer provided on the surface of a portable electronic device component has performance as an antenna can be mentioned.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。 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.
＜樹脂成分＞
Ｓ－３０００Ｆ：三菱エンジニアリングプラスチックス製、芳香族ポリカーボネート樹脂
ＡＴ－０８：日本Ａ＆Ｌ社製、塊状重合させたＡＢＳ樹脂 <Resin component>
S-3000F: manufactured by Mitsubishi Engineering Plastics, aromatic polycarbonate resin AT-08: manufactured by Nippon A & L Co., Ltd., bulk polymerized ABS resin
＜ガラス繊維＞
Ｔ－１８７：日本電気硝子社製、直径が１３μｍ、カット長３ｍｍの円形断面を有するガラス繊維（扁平率１）
３ＰＡ８２０：日東紡績社製、直径２８μｍ、短径７μｍの扁平断面を有するガラス繊維（扁平率４） <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)
3PA820: 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 4)
＜エラストマー＞
Ｓ－２０３０：三菱レイヨン社製、メタクリル酸メチル／アクリル酸メチル／ジメチルシロキサンの共重合体
Ｍ７１１：カネカ社製、ブタジエン系のコアと、アクリル系のシェルとからなるコア／シェル型エラストマー。 <Elastomer>
S-2030: Methyl methacrylate / methyl acrylate / dimethylsiloxane copolymer M711 manufactured by Mitsubishi Rayon Co., Ltd., Kaneka Co., Ltd., core / shell type elastomer comprising a butadiene core and an acrylic shell.
＜ＬＤＳ添加剤＞
Ｂｌａｃｋ１Ｇ：シェパードジャパン社製、スピネル構造の銅クロム酸化物、銅クロム酸化物以外の成分、１質量％以下
２４－３５８８ＰＫ：Ｆｅｒｒｏ社製、スピネル構造の銅クロム酸化物、銅クロム酸化物以外の成分、１質量％以下
２４－３０９７ＰＫ：Ｆｅｒｒｏ社製、スピネル構造の銅クロム酸化物、酸化マンガンを５～７質量％含有 <LDS additive>
Black1G: manufactured by Shepard Japan, a component other than spinel copper chrome oxide, copper chrome oxide, 1% by mass or less 24-3588 PK: manufactured by Ferro, a component other than spinel structured copper chrome oxide, copper chrome oxide 1% by mass or less 24-3097PK: manufactured by Ferro, containing 5-7% by mass of spinel copper chrome oxide and manganese oxide
＜リン系難燃剤＞
＜＜縮合リン酸エステル＞＞
ＰＸ－２００：大八化学工業社製、レゾルシノールビスー２，６－キシレニルホスフェート
ＦＰ－７００：旭電化工業（株）製、アデカスタブＦＰ－７００、２，２－ビス（ｐ－ヒドロキシフェニル）プロパン・トリクロロホスフィンオキシド重縮合物（重合度１～３）のフェノール縮合物 <Phosphorus flame retardant>
<< 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) propane・ Phenol condensate of trichlorophosphine oxide polycondensate (degree of polymerization 1 to 3)
＜＜ホスファゼン化合物＞＞
ＦＰ－１００：伏見製薬社製、フェノキシホスファゼン化合物 << Phosphazene Compound >>
FP-100: Phenoxyphosphazene compound manufactured by Fushimi Pharmaceutical Co., Ltd.
＜ＰＴＦＥ＞
６－Ｊ：三井デュポンフロロケミカル社製、フィブリル形成能を有するフルオロポリマー
＜リン系安定剤＞
ＡＸ－７１：モノ－およびジ－ステアリルアシッドホスフェートのほぼ等モル 混合物（ＡＤＥＫＡ製）
＜酸化防止剤＞
Ｉｒｇ１０７６：ＢＡＳＦ社製、オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４-ヒドロキシフェニル）プロピオネート
＜離型剤＞
ＶＰＧ８６１：コグニスオレオケミカルズジャパン社製、ペンタエリスリトールテトラステアレート <PTFE>
6-J: Mitsui Dupont Fluoro Chemical Co., Ltd., fluoropolymer having fibril forming ability <Phosphorus stabilizer>
AX-71: Almost equimolar mixture of mono- and di-stearyl acid phosphate (manufactured by ADEKA)
<Antioxidant>
Irg1076: manufactured by BASF, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate <release agent>
VPG861: manufactured by Cognis Oleochemicals Japan, pentaerythritol tetrastearate
＜コンパウンド＞
　後述する表に示す組成となるように、各成分をそれぞれ秤量し、タンブラーにて２０分混合した後、１ベントを備えた日本製鋼所社製（ＴＥＸ３０ＨＳＳＴ）に供給し、スクリュー回転数２００ｒｐｍ、吐出量２０ｋｇ／時間、バレル温度３００℃の条件で混練し、ストランド状に押出された溶融樹脂を水槽にて急冷し、ペレタイザーを用いてペレット化し、樹脂組成物のペレットを得た。 <Compound>
Each component was weighed so as to have the composition shown in the table to be described later, mixed in 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 300 ° C. and extruded into a strand shape, was rapidly cooled in a water tank and pelletized using a pelletizer to obtain resin composition pellets.
＜難燃性（ＵＬ９４）＞
　上述の製造方法で得られたペレットを１２０℃で５時間乾燥させた後、日本製鋼所製のＪ５０－ＥＰ型射出成形機を用いて、シリンダー温度２９０℃、金型温度８０℃の条件で射出成形し、長さ１２５ｍｍ、幅１３ｍｍ、厚さ０．８ｍｍのＵＬ試験用試験片を成形した。 <Flame retardancy (UL94)>
The pellets obtained by the above production method were dried at 120 ° C. for 5 hours, and then injected using a J50-EP injection molding machine manufactured by Nippon Steel, under the conditions of a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. A UL test specimen having a length of 125 mm, a width of 13 mm, and a thickness of 0.8 mm was molded.
　各樹脂組成物の難燃性の評価は、上述の方法で得られたＵＬ試験用試験片を温度２３℃、湿度５０％の恒温室の中で４８時間調湿し、米国アンダーライターズ・ラボラトリーズ（ＵＬ）が定めているＵＬ９４試験（機器の部品用プラスチック材料の燃焼試験）に準拠して行なった。ＵＬ９４Ｖとは、鉛直に保持した所定の大きさの試験片にバーナーの炎を１０秒間接炎した後の残炎時間やドリップ性から難燃性を評価する方法であり、Ｖ－０、Ｖ－１及びＶ－２の難燃性を有するためには、以下の表に示す基準を満たすことが必要となる。 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.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　ここで残炎時間とは、着火源を遠ざけた後の、試験片の有炎燃焼を続ける時間の長さである。また、ドリップによる綿着火とは、試験片の下端から約３００ｍｍ下にある標識用の綿が、試験片からの滴下（ドリップ）物によって着火されるかどうかによって決定される。さらに、５試料のうち、１つでも上記基準を満たさないものがある場合、Ｖ－２を満足しないとしてＮＲ（ｎｏｔ　ｒａｔｅｄ）と評価した。 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. Furthermore, if any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) as not satisfying V-2.
＜曲げ弾性率および曲げ強度＞
　上述の製造方法で得られたペレットを１２０℃で５時間乾燥させた後、日精樹脂工業製、ＳＧ７５－ＭＩＩを用いて、シリンダー温度３００℃、金型温度１００℃、成形サイクル５０秒の条件で射出成形し、４ｍｍ厚さのＩＳＯ引張り試験片を成形した。
　ＩＳＯ１７８に準拠して、上記ＩＳＯ引張り試験片（４ｍｍ厚）を用いて、２３℃の温度で曲げ弾性率（単位：ＭＰａ）および曲げ強度（単位：ＭＰａ）を測定した。 <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).
＜シャルピー衝撃強度＞
　上記で得られたＩＳＯ引張り試験片（４ｍｍ厚）を用い、ＩＳＯ１７９に準拠し、２３℃の条件で、ノッチ有シャルピー衝撃強度を測定した。 <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.
＜荷重たわみ温度（ＤＴＵＬ）＞
　上記で得られたＩＳＯ引張り試験片（４ｍｍ厚）を用い、ＩＳＯ７５－１及びＩＳＯ７５－２に準拠して荷重１．８０ＭＰａの条件で荷重たわみ温度を測定した。 <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.
＜メッキ性（ＬＤＳ活性）－Ｐｌａｔｉｎｇ　Ｉｎｄｅｘ＞
　上述の製造方法で得られたペレットを１２０℃で５時間乾燥させた後、日精樹脂工業製、ＳＧ７５－ＭＩＩを用いて、シリンダー温度３００℃、金型温度１００℃、成形サイクル５０秒の条件で射出成形し、３ｍｍ厚さのプレートを成形した。
　上記で得られた３ｍｍ厚のプレートに１０６４ｎｍのＹＡＧレーザーを用い、出力２．６～１３Ｗの範囲のいずれか、速度１～２ｍ／ｓのいずれか、周波数１０～５０μｓの範囲のいずれかの条件から組み合わされた各種条件でレーザー照射により印字し、続いて、試験片を硫酸にて脱脂後、キザイ社製ＴＨＰアルカリアクチ及びＴＨＰアルカリアクセで処理後、キザイ社製ＳＥＬカッパ―にてメッキ処理を行った。メッキ処理後の試験片を目視にて判定し、下記５段階に分類した。
５：各種レーザー条件中、明瞭にメッキが載った条件が７５～１００％
４：各種レーザー条件中、明瞭にメッキが載った条件が５０～７４％
３：各種レーザー条件中、明瞭にメッキが載った条件が３０～４９％
２：各種レーザー条件中、明瞭にメッキが載った条件が１０～２９％
１：各種レーザー条件中、明瞭にメッキが載った条件が１０に満たない <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 300 ° C., the mold temperature was 100 ° 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 either 2.6 to 13 W, the speed was 1 to 2 m / s, or 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.
　結果を下記表に示す。 The results are shown in the table below.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　上記表から明らかなとおり、本発明の組成物を用いた場合は、メッキ性を維持しつつ、曲げ弾性率、曲げ強度、シャルピー衝撃強さや荷重たわみ温度などの各種機械的特性および難燃性に優れた試験片が得られており、比較例の組成物を用いた場合は、これらのいずれかが劣っていた。 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. An excellent test piece was obtained, and any of these was inferior when the composition of the comparative example was used.

Claims (15)

  1. ポリカーボネート樹脂４０～９５質量％およびガラス繊維５～６０質量％を含む成分１００質量部に対し、エラストマー０．５～１０質量部、銅およびクロムを含むレーザーダイレクトストラクチャリング添加剤５～２０質量部、リン系難燃剤５～３０質量部、ならびに、ポリテトラフルオロエチレン０．１～１質量部を含み、
    前記エラストマーは、アクリロニトリル／ブタジエン／スチレン共重合体の含有量が全体の１０質量％未満であり、
    アクリロニトリル／ブタジエン／スチレン共重合体の含有量は、ポリカーボネート樹脂とアクリロニトリル／ブタジエン／スチレン共重合体の合計量の１０質量％未満である、
    レーザーダイレクトストラクチャリング用樹脂組成物。     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 with respect to 100 parts by weight of a component containing 40 to 95% by weight of a polycarbonate resin and 5 to 60% by weight of glass fiber, Including 5 to 30 parts by mass of a phosphorus-based flame retardant, and 0.1 to 1 part by mass of polytetrafluoroethylene,
    The elastomer has an acrylonitrile / butadiene / styrene copolymer content of less than 10% by mass of the total,
    The content of the acrylonitrile / butadiene / styrene copolymer is less than 10% by mass of the total amount of the polycarbonate resin and the acrylonitrile / butadiene / styrene copolymer.
    Resin composition for laser direct structuring.
  2. 前記リン系難燃剤が、縮合リン酸エステルである、請求項１に記載のレーザーダイレクトストラクチャリング用樹脂組成物。 The resin composition for laser direct structuring according to claim 1, wherein the phosphorus-based flame retardant is a condensed phosphate ester.
  3. 前記リン系難燃剤が、ホスファゼン化合物である、請求項１に記載のレーザーダイレクトストラクチャリング用樹脂組成物。 The resin composition for laser direct structuring according to claim 1, wherein the phosphorus flame retardant is a phosphazene compound.
  4. 前記レーザーダイレクトストラクチャリング添加剤が、スピネル構造体である、請求項１～３のいずれか１項に記載のレーザーダイレクトストラクチャリング用樹脂組成物。 The resin composition for laser direct structuring according to any one of claims 1 to 3, wherein the laser direct structuring additive is a spinel structure.
  5. 前記エラストマーが、シロキサン共重合エラストマーである、請求項１～４のいずれか１項に記載のレーザーダイレクトストラクチャリング用樹脂組成物。 The resin composition for laser direct structuring according to any one of claims 1 to 4, wherein the elastomer is a siloxane copolymer elastomer.
  6. 前記ガラス繊維の長さ方向に直角な断面の長径をＤ２、短径をＤ１とするときの長径／短径比（Ｄ２／Ｄ１）で示される扁平率が１．５以下である、請求項１～５のいずれか１項に記載のレーザーダイレクトストラクチャリング用樹脂組成物。 The flatness indicated by a major axis / minor axis ratio (D2 / D1) when the major axis of the cross section perpendicular to the length direction of the glass fiber is D2 and the minor axis is D1 is 1.5 or less. 6. The resin composition for laser direct structuring according to any one of 1 to 5.
  7. 前記ガラス繊維の長さ方向に直角な断面の長径をＤ２、短径をＤ１とするときの長径／短径比（Ｄ２／Ｄ１）で示される扁平率が１．５を超え８．０以下である、請求項１～６のいずれか１項に記載のレーザーダイレクトストラクチャリング用樹脂組成物。 When the major axis of the cross section perpendicular to the length direction of the glass fiber is D2 and the minor axis is D1, the flatness indicated by the ratio of major axis / minor axis (D2 / D1) exceeds 1.5 and is 8.0 or less. The resin composition for laser direct structuring according to any one of claims 1 to 6.
  8. 前記組成物が、アクリロニトリル／ブタジエン／スチレン共重合体を実質的に含まない、請求項１～７のいずれか１項に記載のレーザーダイレクトストラクチャリング用樹脂組成物。 The resin composition for laser direct structuring according to any one of claims 1 to 7, wherein the composition does not substantially contain an acrylonitrile / butadiene / styrene copolymer.
  9. 請求項１～８のいずれか１項に記載のレーザーダイレクトストラクチャリング用樹脂組成物を成形してなる樹脂成形品。 A resin molded product obtained by molding the resin composition for laser direct structuring according to any one of claims 1 to 8.
  10. さらに、表面にメッキ層を有する、請求項９に記載の樹脂成形品。 Furthermore, the resin molded product of Claim 9 which has a plating layer on the surface.
  11. 携帯電子機器部品である、請求項９または１０に記載の樹脂成形品。 The resin molded product according to claim 9 or 10, which is a portable electronic device component.
  12. 前記メッキ層がアンテナとしての性能を保有する、請求項１０または１１に記載の樹脂成形品。 The resin molded product according to claim 10 or 11, wherein the plated layer retains performance as an antenna.
  13. 請求項１～８のいずれか１項に記載のレーザーダイレクトストラクチャリング用樹脂組成物を成形してなる樹脂成形品の表面に、レーザーを照射後、金属を適用して、メッキ層を形成することを含む、メッキ層付樹脂成形品の製造方法。 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.
  14. 前記メッキが銅メッキである、請求項１３に記載のメッキ層付樹脂成形品の製造方法。 The manufacturing method of the resin molded product with a plating layer of Claim 13 whose said plating is copper plating.
  15. 請求項１３または１４に記載のメッキ層付樹脂成形品の製造方法を含む、アンテナを有する携帯電子機器部品の製造方法。 The manufacturing method of the portable electronic device component which has an antenna including the manufacturing method of the resin molded product with a plating layer of Claim 13 or 14.
PCT/JP2013/084780 2013-01-24 2013-12-26 Resin composition for laser direct structuring, molded resin article, and method of manufacturing molded resin article having plating film WO2014115475A1 (en)

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