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WO2014115475A1 - Composition de résine pour structuration directe par laser, article en résine moulée, et procédé de fabrication dudit article en résine moulée comprenant un film de placage - Google Patents

Composition de résine pour structuration directe par laser, article en résine moulée, et procédé de fabrication dudit article en résine moulée comprenant un film de placage 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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Prior art keywords
mass
resin composition
group
laser direct
resin
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PCT/JP2013/084780
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English (en)
Japanese (ja)
Inventor
庄司　英和
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Mitsubishi Engineering Plastics Corp
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Mitsubishi Engineering Plastics Corp
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Priority to CN201380071268.8A priority Critical patent/CN104955896B/zh
Priority to JP2014519737A priority patent/JP5615992B1/ja
Publication of WO2014115475A1 publication Critical patent/WO2014115475A1/fr
Anticipated expiration legal-status Critical
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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.

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Abstract

La présente invention concerne une composition de résine présentant des propriétés de placage constantes ainsi qu'une excellente ininflammabilité et diverses propriétés mécaniques telles qu'un module de courbure, une résistance à la flexion, une résistance aux chocs selon Charpy, et une température de fléchissement sous charge. Ladite composition de résine destinée à une structuration directe par laser selon l'invention contient, par rapport aux 100 parties en masse d'un constituant contenant de 40 à 95 % en masse d'une résine polycarbonate et de 5 à 60 % en masse d'une fibre de verre, de 0,5 à 10 parties en masse d'un élastomère, de 5 à 20 parties en masse d'un additif de structuration directe par laser contenant du cuivre et du chrome, de 5 à 30 parties en masse d'un agent ignifugeant à base de phosphore, et de 0,1 à 1 partie en masse de polytétrafluoroéthylène. Ledit élastomère contient moins de 10 % en masse de copolymère acrylonitrile/butadiène/styrène, et la quantité de copolymère acrylonitrile/butadiène/styrène est inférieure à 10 % en masse de la teneur totale en résine polycarbonate et en copolymère acrylonitrile/butadiène/styrène.
PCT/JP2013/084780 2013-01-24 2013-12-26 Composition de résine pour structuration directe par laser, article en résine moulée, et procédé de fabrication dudit article en résine moulée comprenant un film de placage Ceased WO2014115475A1 (fr)

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WO2021241870A1 (fr) * 2020-05-27 2021-12-02 롯데케미칼 주식회사 Composition de résine thermoplastique pour un procédé de structuration directe par laser et produit moulé la comprenant
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CN115702208A (zh) * 2020-05-27 2023-02-14 乐天化学株式会社 用于激光直接结构化工艺的热塑性树脂组合物及包含它的成型品
WO2022050424A1 (fr) 2020-09-07 2022-03-10 デンカ株式会社 Corps moulé plaqué de composition de résine thermoplastique
WO2024206154A1 (fr) * 2023-03-24 2024-10-03 Covestro Llc Emballage de stabilisation thermique pour mélanges polycarbonate/acrylonitrile-butadiène-styrène

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