Polycarbonate resin composition

Abstract

To provide a polycarbonate resin composition that exhibits superior laser direct structuring performance, thermal conductivity, and impact resistance, while having a low dielectric loss tangent.SOLUTION: A polycarbonate resin composition containing, relative to 100 pts.mass of a polycarbonate resin (A), 15 to 60 pts.mass of plate-like alumina (B), 15 to 60 pts.mass of another filler (C) other than (B), and 0.5 to 50 pts.mass of a laser direct structuring additive (D), wherein the mass ratio (C) / (B) of the content of the other filler (C) to the plate-like alumina (B) is 0.5 or more, and the mass ratio (B) / (D) of the content of the plate-like alumina (B) to the laser direct structuring additive (D) is 6 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition having excellent plating properties, thermal conductivity, and impact resistance and a low dielectric loss tangent, and a molded article thereof. [Background technology]

[0002] Polycarbonate resins have excellent impact resistance, heat resistance, electrical insulation, dimensional stability, and other properties, and because they have a good balance of these properties, they are widely used in fields such as electrical and electronic equipment parts, office automation equipment parts, precision machinery parts, and vehicle parts.

[0003] In the above fields, most devices are equipped with heat-generating components. In recent years, as devices have become smaller, lighter, and more sophisticated, such as with higher transmission density, the amount of power consumed per component has increased, and the number of components that generate a lot of heat and are small and lightweight has increased. This has created a strong demand for polycarbonate resin materials that have high thermal conductivity while also providing excellent insulation and strength.

[0004] As a method for imparting thermal conductivity to a polycarbonate resin material, a method of blending various thermally conductive fillers is known, and Patent Documents 1 to 6 describe polycarbonate resin compositions with good thermal conductivity. Furthermore, Patent Document 7 proposes that a resin composition containing plate-like alumina has excellent physical properties such as mechanical properties while maintaining transparency, and is therefore suitable for use as organic glass for automobiles. However, the resin composition containing plate-like alumina has a problem in that it has low thermal conductivity. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-16093 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-238917 [Patent Document 3] Japanese Patent Application Laid-Open No. 2008-127554 [Patent Document 4] Japanese Patent Application Laid-Open No. 2008-163270 [Patent Document 5] Japanese Patent Application Laid-Open No. 2009-161582 [Patent Document 6] Japanese Patent Application Laid-Open No. 2011-16936 [Patent Document 7] Patent No. 4556628 Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, a technique called laser direct structuring (hereinafter referred to as "LDS") has been attracting attention. This is a method in which a laser is irradiated onto the surface of a resin molded product containing an LDS additive, activating only the laser-irradiated areas, and then metal plating is applied to these activated areas. This method allows metal parts such as antennas to be formed directly on the surface of a resin substrate without the use of adhesives, making it suitable for use in components for mobile phones, for example. Materials that make up antennas are required to have a low dielectric tangent, and a low dielectric tangent minimizes energy loss. An object (object) of the present invention is to provide a polycarbonate resin composition that is excellent in plating property, thermal conductivity, and impact resistance and has a low dielectric loss tangent. [Means for solving the problem]

[0007] As a result of extensive investigations into solving the above-mentioned problems, the present inventors have found that a polycarbonate resin composition that solves the above-mentioned problems can be obtained by containing platelet alumina, another filler, and an LDS additive, and by setting the mass ratio of the other filler to the platelet alumina content and the mass ratio of the platelet alumina to the LDS additive content within specific ranges, and have completed the present invention. The present invention provides the following polycarbonate resin composition and molded article.

[0008] 1. A polycarbonate resin composition comprising, relative to 100 parts by mass of polycarbonate resin (A), 15 to 60 parts by mass of plate-like alumina (B), 15 to 60 parts by mass of a filler (C) other than (B), and 0.5 to 50 parts by mass of a laser direct structuring additive (D), wherein the mass ratio (C) / (B) of the other filler (C) to the plate-like alumina (B) is 0.5 or more, and further the mass ratio (B) / (D) of the plate-like alumina (B) to the laser direct structuring additive (D) is 6 or less. 2. The polycarbonate resin composition according to the above item 1, wherein the other filler (C) is talc. 3. The polycarbonate resin composition according to 1 or 2 above, wherein the plate-like alumina (B) has an aspect ratio of 5 to 60. 4. The polycarbonate composition according to any one of the above 1 to 3, further comprising 0.5 to 10 parts by mass of a maleic anhydride olefin copolymer per 100 parts by mass of the polycarbonate resin (A). 5. The polycarbonate composition according to any one of the above 1 to 4, further comprising 0.01 to 10 parts by mass of an elastomer per 100 parts by mass of the polycarbonate resin (A). 6. The polycarbonate resin composition according to any one of 1 to 5 above, which is for use in a thermally conductive molded article. 7. The polycarbonate resin composition according to any one of 1 to 6 above, which is for use in a laser direct structuring molded product. 8. Pellets of the polycarbonate resin composition according to any one of 1 to 7 above. 9. A molded article made from the polycarbonate resin composition according to any one of 1 to 7 above. 10. A molded article made from pellets of the polycarbonate resin composition described in 8 above. [Effects of the Invention]

[0009] The polycarbonate resin composition of the present invention has excellent plating properties, excellent thermal conductivity and impact resistance, and a low dielectric loss tangent, and is therefore particularly suitable for use as parts for various electrical and electronic devices. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below by showing embodiments and examples, but the present invention is not limited to the embodiments and examples shown below, and can be modified and implemented as desired within the scope that does not deviate from the gist of the present invention.

[0011] The polycarbonate resin composition of the present invention contains, relative to 100 parts by mass of polycarbonate resin (A), 15 to 60 parts by mass of plate-like alumina (B), 15 to 60 parts by mass of a filler (C) other than (B), and 0.5 to 50 parts by mass of a laser direct structuring additive (D), wherein the mass ratio (C) / (B) of the other filler (C) to the plate-like alumina (B) is 0.5 or more, and the mass ratio (B) / (D) of the plate-like alumina (B) to the laser direct structuring additive (D) is 6 or less.

[0012] [Polycarbonate resin (A)] The type of polycarbonate resin (A) contained in the resin composition of the present invention is not particularly limited, and various types can be used. Polycarbonate resins can be classified into aromatic polycarbonate resins in which the carbons directly bonded to carbonate bonds are aromatic carbons, and aliphatic polycarbonate resins in which the carbons directly bonded to carbonate bonds are aliphatic carbons, and either can be used, but aromatic polycarbonate resins are preferred as the polycarbonate resin (A) from the viewpoints of heat resistance, mechanical properties, electrical properties, etc.

[0013] Among the monomers that are raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include: dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (i.e., resorcinol), and 1,4-dihydroxybenzene; dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, and 4,4'-dihydroxybiphenyl;

[0014] dihydroxynaphthalenes such as 2,2'-dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene;

[0015] dihydroxydiaryl ethers such as 2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis(3-hydroxyphenoxy)benzene, and 1,3-bis(4-hydroxyphenoxy)benzene;

[0016] 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A), 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C), 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-methoxy-4-hydroxyphenyl)propane, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-cyclohexyl-4-hydroxyphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)(4-propenylphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-naphthylethane, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)hexane, 1,1-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)octane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)nonane, 1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(4-hydroxyphenyl)dodecane, Bis(hydroxyaryl)alkanes such as;

[0017] 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,4-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-propyl-5-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-tert-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-tert-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane, 1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexane, Bis(hydroxyaryl)cycloalkanes such as;

[0018] 9,9-bis(4-hydroxyphenyl)fluorene, Cardo structure-containing bisphenols such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene;

[0019] 4,4'-dihydroxydiphenyl sulfide, Dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; 4,4'-dihydroxydiphenyl sulfone, dihydroxydiarylsulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone; etc.

[0020] Of these, bis(hydroxyaryl)alkanes are preferred, and bis(4-hydroxyphenyl)alkanes are particularly preferred. In particular, from the standpoints of impact resistance and heat resistance, 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A) and 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C) are preferred. The aromatic dihydroxy compounds may be used alone or in any combination of two or more in any ratio.

[0021] Among the monomers that serve as raw materials for polycarbonate resins, examples of carbonate precursors include carbonyl halides, carbonate esters, etc. The carbonate precursors may be used alone or in any combination and ratio of two or more.

[0022] Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformates of dihydroxy compounds and monochloroformates of dihydroxy compounds; and the like.

[0023] Specific examples of carbonate esters include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, and carbonates of dihydroxy compounds such as cyclic carbonates.

[0024] The method for producing the polycarbonate resin (A) is not particularly limited, and any method can be used. Examples include interfacial polymerization, melt transesterification, pyridine method, ring-opening polymerization of a cyclic carbonate compound, and solid-phase transesterification of a prepolymer. Among these, the interfacial polymerization method is particularly preferred.

[0025] Furthermore, the polycarbonate resin (A) may be not only virgin raw materials but also polycarbonate resin recycled from used products (so-called material-recycled polycarbonate resin), and it is preferable to contain both virgin raw materials and recycled resin, or it may be made of recycled polycarbonate resin. The proportion of recycled polycarbonate resin in the polycarbonate resin (A) is preferably 40% or more, 50% or more, 60% or more, or 80% or more, and it is also preferable that the recycled polycarbonate resin is 100%.

[0026] The molecular weight of the polycarbonate resin (A), expressed as a viscosity-average molecular weight (Mv) calculated from the solution viscosity measured at 25°C using methylene chloride as a solvent, is preferably 10,000 to 50,000, more preferably 10,000 to 40,000, even more preferably 10,000 to 30,000 or 10,000 to 26,000, and even more preferably 10,500 or more, 11,000 or more, particularly preferably 11,500 or more, most preferably 12,000 or more, and even more preferably 25,000 or less, particularly preferably 24,000 or less. By setting the viscosity-average molecular weight to at least the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, and by setting the viscosity-average molecular weight to at most the upper limit of the above range, the decrease in flowability of the polycarbonate resin composition of the present invention can be suppressed and improved, and molding processability can be improved, allowing for easier molding processability. Two or more polycarbonate resins having different viscosity average molecular weights may be mixed together, and in this case, polycarbonate resins having viscosity average molecular weights outside the above-mentioned preferred range may be mixed.

[0027] The viscosity average molecular weight [Mv] is calculated by using methylene chloride as a solvent and an Ubbelohde viscometer to determine the intrinsic viscosity [η] (unit: dl / g) at a temperature of 25°C, and then calculating it using the Schnell viscosity formula, i.e., η = 1.23 × 10 -4 Mv 0.83 The intrinsic viscosity [η] is the specific viscosity [η] at each solution concentration [C] (g / dl). sp ] was measured and the value was calculated according to the following formula.

number

[0028] Furthermore, in order to improve the appearance and flowability of the molded article, the polycarbonate resin (A) may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and usually 9500 or less, preferably 9000 or less. The amount of the polycarbonate oligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

[0029] [Plate alumina (B)] The polycarbonate resin composition of the present invention contains plate-like alumina (B). Here, "plate-like" means that the aspect ratio, calculated by dividing the average particle diameter by the thickness, is preferably 2 or more.

[0030] The plate-like alumina (B) preferably has an average thickness of 0.02 to 2 μm. Having the average thickness of the plate-like alumina in this range is preferred because it allows the mechanical strength of a molded article of the polycarbonate resin composition to be increased, such as flexural modulus, flexural strength, tensile strength, and tensile modulus. The average thickness of the plate-like alumina is more preferably 0.02 to 1 μm, even more preferably 0.03 to 0.5 μm, and particularly preferably 0.05 to 0.3 μm.

[0031] The plate-like alumina (B) preferably has an aspect ratio (= average particle diameter L of plate-like alumina / average thickness D of plate-like alumina), which is the ratio of the average particle diameter to the average thickness, of 5 to 60. An aspect ratio in this range is preferred because the resin composition has excellent mechanical strength. The aspect ratio is more preferably 10 to 50, and even more preferably 15 to 50.

[0032] The average particle size of the plate-like alumina (B) is preferably 0.5 to 100 μm, more preferably 1 to 50 μm.

[0033] The plate-like alumina (B) may be in the form of a circular plate or an elliptical plate, but the particle shape is preferably a polygonal plate, for example, hexagonal to octagonal, from the viewpoint of ease of handling and production.

[0034] In this specification, the average thickness of the plate-like alumina is the arithmetic mean value of the thicknesses measured for at least 50 randomly selected plate-like alumina particles from an image obtained by a scanning electron microscope (SEM). The average particle diameter of the plate-like alumina is the volume-based median diameter D from the volume-based cumulative particle size distribution measured by a laser diffraction / scattering particle size distribution analyzer. 50 The value calculated as follows:

[0035] The alumina contained in the plate alumina (B) is aluminum oxide, and may be transition alumina of various crystalline forms such as γ, δ, θ, and κ, or may contain alumina hydrate in the transition alumina, but is preferably in the α-crystalline form (α-type) in terms of superior mechanical strength and thermal conductivity. The α-crystalline form is a dense crystalline structure of alumina, and is advantageous for improving the mechanical strength and thermal conductivity of the plate alumina. The plate-like alumina (B) may contain molybdenum and may further contain impurities from the raw materials or shape control agents, etc., as long as the effects of the present invention are not impaired.

[0036] Plate-like alumina can be produced by known and commonly used production methods such as a hydrothermal method and a flux method. Among these, a preferred production method is a method for producing alumina particles in which an aluminum compound is fired in the presence of a shape control agent consisting of a molybdenum compound and silicon or a compound containing a silicon atom.

[0037] The content of the plate-like alumina (B) is 15 to 60 parts by mass per 100 parts by mass of the polycarbonate resin (A). By combining the polycarbonate resin (A) in such an amount with a specific amount of filler (C) other than the plate-like alumina (B), a resin composition can be obtained that is excellent in all of the thermal conductivity, self-tapping property, and insulating property in a well-balanced manner. If the content of the plate-like alumina (B) is less than 15 parts by mass, the thermal conductivity becomes insufficient. Conversely, if it exceeds 60 parts by mass, the strength and fluidity tend to be insufficient. The content of the plate-like alumina (B) is preferably 16 parts by mass or more, and preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less.

[0038] Other Fillers The polycarbonate resin composition of the present invention contains a filler (C) other than the plate-like alumina (B). The content of the other filler (C) is 15 to 60 parts by mass per 100 parts by mass of the polycarbonate resin (A), and the mass ratio (C) / (B) of the content of the other filler (C) to the plate-like alumina (B) is 0.5 or more. By combining the other filler (C) with the plate-like alumina (B) in such an amount and ratio, the thermal conductivity and mechanical strength such as impact resistance of the polycarbonate resin composition can be improved, and a low dielectric tangent can be achieved.

[0039] The other filler (C) is a filler other than the plate-like alumina (B), and is preferably an inorganic filler. The form of the other filler (C) may be any of spherical, plate-like, needle-like, fibrous, etc., but plate-like, needle-like, and fibrous forms are preferred in order to improve the dimensional stability, heat resistance, and rigidity of the final resin composition.

[0040] Specific examples of such plate-like, needle-like, and fibrous inorganic fillers include: plate-like fillers such as magnesium silicate such as talc, boron nitride, mica, glass flakes, graphite, sericite, clay, montmorillonite, and plate-like calcium carbonate; needle-like fillers such as calcium silicate such as wollastonite, xonotlite, calcium titanate, aluminum borate, and plate-like calcium carbonate; and fibrous fillers such as glass fiber and carbon fiber, as well as spherical alumina. Among these inorganic fillers, talc, boron nitride, mica, glass flakes, glass fiber, and carbon fiber are preferred in terms of synergistic effects with the plate-like alumina (B), with talc being particularly preferred.

[0041] The average particle size of the other filler (C) is preferably 0.1 to 25 μm, more preferably 0.5 to 15 μm, in the case of fillers other than plate-like, needle-like fillers and fibrous fillers. Here, the average particle size is the median value (D 50 ) In addition, for example, in the case of talc supplied as a product, the average particle size as a product standard can also be adopted. The fiber diameter of the fibrous filler is preferably 1 to 15 μm.

[0042] The other filler (C) may be untreated, or may be surface-treated with an inorganic surface treatment agent, a derivative of a higher fatty acid or its ester salt, or a coupling agent such as aminosilane or epoxysilane to enhance affinity or interfacial bonding with the polycarbonate resin, or may be bundled with an acrylic resin or urethane resin to improve handleability. When surface-treating, it is preferable to also treat with various surfactants, such as nonionic, cationic, or anionic surfactants, or various dispersants, such as resins, from the viewpoint of improving mechanical strength and kneadability. There are no particular restrictions on the method for pulverizing inorganic fillers such as talc from raw ore, but from the viewpoint of handleability, an aggregated state with increased bulk density is preferred. Examples of preferred inorganic fillers include deaerated and compressed talc (compressed talc) and granulated talc using a binder (granular talc).

[0043] As described above, the content of the other filler (C) is 15 to 60 parts by mass per 100 parts by mass of the polycarbonate resin (A), and the mass ratio (C) / (B) of the content is 0.5 or more, but is more preferably 25 parts by mass or more, more preferably 55 parts by mass or less, and more preferably 50 parts by mass or less. The mass ratio (C) / (B) of the content is preferably 0.55 or more, and preferably 1.8 or less, especially 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, and particularly 1.3 or less.

[0044] [Laser Direct Structuring Additive (D)] The resin composition of the present invention contains a laser direct structuring additive (D). When irradiated with a laser beam, the metal atoms of the LDS additive are activated to form a metal layer on the surface. Preferred examples of the LDS additive (D) include heavy metal composite oxide spinels such as copper chromium oxide (CuCr2O4); copper salts such as copper hydroxide phosphate, copper phosphate, copper sulfate, and copper thiocyanate; zinc oxide, aluminum-doped or antimony-doped zinc oxide; and antimony-containing tin oxides such as tin oxide and tin oxide doped with antimony oxide. Of these, zinc oxide, copper chromium oxide, or antimony-doped tin oxide is more preferred. Furthermore, copper chromium oxide also functions as a black pigment and is therefore suitable for obtaining black molded products, and antimony-containing tin oxide can be used as a white pigment and can therefore be used to obtain white molded products or to produce desired color variations by combining it with pigments of other colors. The average particle size of the LDS additive (D) is preferably 0.01 to 50 μm, more preferably 0.05 to 30 μm. By adjusting the average particle size to such an extent, the uniformity of the plating surface state when plating is applied tends to be improved.

[0045] The content of the LDS additive (D) is 0.5 to 50 parts by mass, preferably 0.7 parts by mass or more, more preferably 1 part by mass or more, and preferably 40 parts by mass or less, especially 30 parts by mass or less, 20 parts by mass or less, 15 parts by mass or less, and particularly preferably 10 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin (A).

[0046] In the present invention, the mass ratio (B) / (D) of the content of the plate-like alumina (B) to the LDS additive (D) is set to 6 or less. By combining with the plate-like alumina (B) at such a ratio, the plating property (LDS property) of the polycarbonate resin composition can be improved. The mass ratio (B) / (D) of the content is preferably 5 or less, more preferably 4.5 or less, and particularly 4.0 or less, and is preferably 1.5 or more, more preferably 2.0 or more, and particularly preferably 2.5 or more.

[0047] [Pigment] The resin composition of the present invention may contain a white pigment. In the present invention, the addition of a white pigment makes it possible to color the resin molded product. Examples of the white pigment include zinc sulfide, zinc oxide, and titanium oxide, and zinc sulfide and titanium oxide are preferred. When the resin composition of the present invention contains a white pigment, the amount of the white pigment is preferably 0.1 to 15 parts by weight, more preferably 1 to 12 parts by weight, and even more preferably 2 to 10 parts by weight, per 100 parts by weight of the resin component. The resin composition of the present invention may contain only one type of white pigment, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0048] [Maleic anhydride olefin copolymer] The resin composition of the present invention also preferably contains a maleic anhydride olefin copolymer. By containing a maleic anhydride olefin copolymer together with the components described above and below, the thermal stability and mechanical properties of the resin composition can be improved, and impact resistance can be further improved.

[0049] As the maleic anhydride olefin copolymer, an olefin-maleic anhydride copolymer or a maleic anhydride-modified olefin polymer is preferred.

[0050] Olefin-maleic anhydride copolymers include copolymers of maleic anhydride and α-olefins. Preferred examples of the α-olefin include α-olefins having 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene-1, and 1-decene, and these may be used alone or in combination. Among these, ethylene, propylene, butene-1, hexene-1, and octene-1 are more preferred, and a combination of ethylene with propylene, butene-1, hexene-1, or octene-1 is particularly preferred. As the olefin-maleic anhydride copolymer, maleic anhydride-ethylene-propylene copolymer and maleic anhydride-ethylene-butene-1 copolymer are particularly preferred.

[0051] The maleic anhydride-modified olefin polymer is obtained by graft-modifying the above-mentioned olefin polymer with maleic anhydride. The graft-modification can be carried out by a known method. For example, a predetermined amount of unsaturated carboxylic acid can be mixed with a molten olefin polymer using an extruder to cause a reaction. The amount of maleic anhydride to be grafted is usually in the range of 0.005 to 25% by mass, preferably 0.01 to 20% by mass, based on 100% by mass of the maleic anhydride-modified olefin polymer.

[0052] The content of the maleic anhydride olefin copolymer is preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the polycarbonate resin (A). This range further improves impact resistance. The content of the maleic anhydride olefin copolymer is more preferably 1 part by mass or more, even more preferably 1.5 parts by mass, more preferably 7 parts by mass or less, even more preferably 7 parts by mass or less, of which 5 parts by mass or less, and particularly preferably 3 parts by mass or less.

[0053] [Flame retardant] The polycarbonate resin composition of the present invention preferably contains a flame retardant, and the flame retardant is preferably a phosphorus-based flame retardant. The phosphorus-based flame retardant is a compound containing phosphorus in the molecule, and may be a low molecular weight compound, an oligomer, or a polymer. However, from the viewpoint of thermal stability, for example, a phosphate ester compound represented by the following general formula (1) or a phosphazene compound represented by the following general formula (2) or (3) is preferred.

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] <Phosphate ester compounds> The phosphate ester compound represented by the general formula (1) may be a mixture of compounds having different k values, and in the case of a mixture of condensed phosphate esters having different k values, k is the average value of the mixture. k is usually an integer of 0 to 5, and in the case of a mixture of compounds having different k values, the average k value is preferably 0.5 to 2, more preferably 0.6 to 1.5, even more preferably 0.8 to 1.2, and particularly preferably 0.95 to 1.15.

[0058] Also, X 1 represents a divalent arylene group, such as a divalent group derived from a dihydroxy compound such as resorcinol, hydroquinone, bisphenol A, 2,2'-dihydroxybiphenyl, 2,3'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, or 2,7-dihydroxynaphthalene. Of these, divalent groups derived from resorcinol, bisphenol A, or 3,3'-dihydroxybiphenyl are particularly preferred.

[0059] In addition, p, q, r and s in the general formula (1) each represent 0 or 1, with 1 being preferred.

[0060] Also, R 1 , R 2 , R 3 and R 4and respectively represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. Examples of such an aryl group include a phenyl group, a cresyl group, a xylyl group, an isopropylphenyl group, a butylphenyl group, a tert-butylphenyl group, a di-tert-butylphenyl group, and a p-cumylphenyl group, with the phenyl group, the cresyl group, and the xylyl group being more preferred.

[0061] Specific examples of the phosphoric acid ester compound represented by general formula (1) include aromatic phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tert-butylphenyl diphenyl phosphate, bis-(tert-butylphenyl)phenyl phosphate, tris-(tert-butylphenyl)phosphate, isopropylphenyl diphenyl phosphate, bis-(isopropylphenyl)diphenyl phosphate, and tris-(isopropylphenyl)phosphate; and condensed phosphoric acid esters such as resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate, bisphenol A bis-diphenyl phosphate, and biphenyl bis-diphenyl phosphate.

[0062] The acid value of the phosphate ester compound represented by general formula (1) is preferably 0.2 mgKOH / g or less, more preferably 0.15 mgKOH / g or less, even more preferably 0.1 mgKOH / g or less, and particularly preferably 0.05 mgKOH / g or less. The lower limit of the acid value can be set to substantially 0. The content of the half ester is more preferably 1.1 parts by mass or less, even more preferably 0.9 parts by mass or less. If the acid value exceeds 0.2 mgKOH / g or the content of the half ester exceeds 1.1 parts by mass, the thermal stability and hydrolysis resistance of the polycarbonate resin composition of the present invention tend to be reduced.

[0063] In addition to the above, the phosphate ester compounds used in the present invention naturally also include 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,3-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,4-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and polyester resins, polycarbonate resins, and epoxy resins containing a phosphate ester moiety.

[0064] <Phosphazene compounds> Examples of the phosphazene compound represented by the general formula (2) or (3) include cyclic and / or chain C phosphazenes such as phenoxyphosphazene, (poly)tolyloxyphosphazene (e.g., o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene, o,m-tolyloxyphosphazene, o,p-tolyloxyphosphazene, m,p-tolyloxyphosphazene, o,m,p-tolyloxyphosphazene, etc.), and (poly)xylyloxyphosphazene. 1-6 Alkyl C 6-20 Cyclic and / or chain C phosphazenes such as aryloxyphosphazenes, (poly)phenoxytolyloxyphosphazenes (e.g., phenoxy o-tolyloxyphosphazene, phenoxy m-tolyloxyphosphazene, phenoxy p-tolyloxyphosphazene, phenoxy o,m-tolyloxyphosphazene, phenoxy o,p-tolyloxyphosphazene, phenoxy m,p-tolyloxyphosphazene, phenoxy o,m,p-tolyloxyphosphazene, etc.), (poly)phenoxyxylyloxyphosphazene, and (poly)phenoxytolyloxyxylyloxyphosphazene. 6-20 Aryl C 1-10 Alkyl C 6-20 Examples include aryloxyphosphazenes. Among these, cyclic and / or chain phenoxyphosphazenes, cyclic and / or chain C 1-3 Alkyl C 6-20 Aryloxyphosphazene, C 6-20 Aryloxy C1-3 Alkyl C 6-20 Aryloxyphosphazenes (for example, cyclic and / or chain tolyloxyphosphazene, cyclic and / or chain phenoxytolylphenoxyphosphazene, etc.).

[0065] The cyclic phosphazene compound represented by the general formula (2) includes R 5 and R 6 may be the same or different and represent an aryl group or an alkylaryl group. Examples of such an aryl group or alkylaryl group include a phenyl group, a naphthyl group, a methylphenyl group, and a benzyl group. Among these, R 5 and R 6 Cyclic phenoxyphosphazenes in which is a phenyl group are particularly preferred. Examples of such cyclic phenoxyphosphazene compounds include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decafenoxycyclopentaphosphazene, which are obtained by isolating cyclic chlorophosphazenes such as hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, and decachlorocyclopentaphosphazene from a mixture of cyclic and linear chlorophosphazenes obtained by reacting ammonium chloride with phosphorus pentachloride at a temperature of 120 to 130°C, and then substituting the cyclic chlorophosphazenes with phenoxy groups.

[0066] In general formula (2), t represents an integer of 3 to 25, and among these, compounds in which t is an integer of 3 to 8 are preferred, and a mixture of compounds with different t's may also be used. Among these, a mixture of compounds in which t=3 accounts for 50% by mass or more, t=4 accounts for 10 to 40% by mass, and t=5 or more accounts for 30% by mass or less in total is preferred.

[0067] In general formula (3), R 7 and R 8 may be the same or different and represent an aryl group or an alkylaryl group. Examples of such an aryl group or alkylaryl group include a phenyl group, a naphthyl group, a methylphenyl group, and a benzyl group. 7 and R8 A chain phenoxyphosphazene in which is a phenyl group is particularly preferred. Examples of such chain phenoxyphosphazene compounds include compounds obtained by ring-opening polymerization of hexachlorocyclotriphosphazene obtained by the above method at a temperature of 220 to 250°C, and substituting the resulting linear dichlorophosphazene having a degree of polymerization of 3 to 10,000 with a phenoxy group.

[0068] Also, R 9 is -N=P(OR 7 ) 3 groups, -N=P(OR 8 ) 3 groups, -N=P(O)OR 7 Group, -N=P(O)OR 8 R represents at least one selected from the group 10 is -P(OR 7 ) 4 groups, -P(OR 8 ) 4 groups, -P(O)(OR 7 ) 2 groups, -P(O)(OR 8 ) represents at least one selected from the following two groups.

[0069] In the general formula (3), u represents an integer of 3 to 10,000, preferably 3 to 1,000, more preferably 3 to 100, and even more preferably 3 to 25.

[0070] The phosphazene compound used in the present invention may be a crosslinked phosphazene compound in which a portion of the compound is crosslinked. The presence of such a crosslinked structure tends to improve heat resistance. Examples of such crosslinked phosphazene compounds include those having a crosslinked structure represented by the following general formula (4), for example, compounds having a crosslinked structure of a 4,4'-diphenylene group, such as a compound having a crosslinked structure of 4,4'-sulfonyldiphenylene (bisphenol S residue), a compound having a crosslinked structure of a 2,2-(4,4'-diphenylene)isopropylidene group, a compound having a crosslinked structure of a 4,4'-oxydiphenylene group, and a compound having a crosslinked structure of a 4,4'-thiodiphenylene group.

[0071] [ka] [In formula (4), X 2 is —C(CH3)2—, —SO2—, —S—, or —O—, and v is 0 or 1.

[0072] The crosslinked phosphazene compound is a compound represented by the general formula (2) in which R 5 and R 6 a bridged phenoxyphosphazene compound in which a cyclic phenoxyphosphazene compound in which R is a phenyl group is bridged by a bridge group represented by the general formula (4), or 7 and R 8 A bridged phenoxyphosphazene compound obtained by crosslinking a chain phenoxyphosphazene compound in which R is a phenyl group with a crosslinking group represented by the above general formula (4) is preferred from the viewpoint of flame retardancy, and a bridged phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound with a crosslinking group represented by the above general formula (4) is more preferred.

[0073] The content of phenylene groups in the bridged phenoxyphosphazene compound is usually 50 to 99.9%, preferably 70 to 90%, based on the total number of phenyl groups and phenylene groups in the cyclic phosphazene compound represented by general formula (2) and / or the chain phenoxyphosphazene compound represented by general formula (3). It is particularly preferred that the bridged phenoxyphosphazene compound is a compound having no free hydroxyl groups in its molecule.

[0074] In the present invention, the phosphazene compound is preferably at least one selected from the group consisting of cyclic phenoxyphosphazene compounds represented by the general formula (2) and crosslinked phenoxyphosphazene compounds obtained by crosslinking a chain phenoxyphosphazene compound represented by the general formula (3) with a crosslinking group, from the viewpoint of flame retardancy and mechanical properties.

[0075] The content of the phosphorus-based flame retardant is preferably 2 to 20 parts by mass relative to 100 parts by mass of the polycarbonate resin (A). If the amount of the phosphorus-based flame retardant is less than 2 parts by mass, the flame retardancy is likely to be insufficient, whereas if it exceeds 20 parts by mass, the heat resistance and mechanical properties are likely to be reduced.

[0076] [Flame retardant synergist] The polycarbonate resin composition of the present invention preferably contains a flame retardant aid. In the present invention, the flame retardant aid refers to a compound that exerts a synergistic effect when used in combination with a phosphorus-based flame retardant used to make the polycarbonate resin flame retardant. The flame retardant aid may be an organic flame retardant aid or an inorganic flame retardant aid.

[0077] As the organic flame retardant auxiliary, fluororesins are preferred, and among them, polytetrafluoroethylene is more preferred. Examples of inorganic flame retardant aids include boric acid compounds such as zinc borate and barium borate, tin compounds such as tin dioxide and zinc stannate, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, antimony compounds such as antimony trioxide, antimony tetraoxide, antimony pentoxide, antimony halides and sodium antimonate, and molybdenum compounds such as molybdenum oxide, among which boric acid compounds are preferred, and zinc borate is particularly preferred. By using a phosphorus-based flame retardant in combination with a flame retardant aid, it is possible to achieve UL-94 V-0 even with thinner walls and shorten the burning time.

[0078] The content of the flame retardant aid is preferably 0.1 to 5 parts by mass, more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more, and more preferably 4 parts by mass or less, still more preferably 3 parts by mass or less, and particularly preferably 2 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin (A). By having the content within the above range, it becomes possible to achieve V-0 in UL-94 even with thinner walls, and to shorten the burning time.

[0079] [Stabilizer] The polycarbonate resin composition of the present invention preferably contains a stabilizer, and the stabilizer is preferably a phosphorus-based stabilizer (antioxidant) or a phenol-based stabilizer (antioxidant).

[0080] Any known phosphorus-based stabilizer can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; metal acid pyrophosphates such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; phosphates of Group 1 or Group 2 metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds, with organic phosphite compounds being particularly preferred.

[0081] Examples of organic phosphite compounds include triphenyl phosphite, tris(mononylphenyl)phosphite, tris(mononyl / dinonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, monooctyldiphenyl phosphite, dioctylmonophenyl phosphite, monodecyldiphenyl phosphite, didecylmonophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, and 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite. Specific examples of such organic phosphite compounds include "ADK STAB 1178," "ADK STAB 2112," and "ADK STAB HP-10" manufactured by ADEKA CORPORATION, "JP-351," "JP-360," and "JP-3CP" manufactured by Johoku Chemical Industry Co., Ltd., and "IRGAFOS 168" manufactured by BASF. The phosphorus-based stabilizer may be contained either as one type or as two or more types in any combination and ratio.

[0082] The content of the phosphorus-based stabilizer is preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, and usually 1 part by mass or less, preferably 0.7 part by mass or less, more preferably 0.5 part by mass or less, relative to 100 parts by mass of the polycarbonate resin (A). If the content of the phosphorus-based stabilizer is below the lower limit of the above range, the thermal stabilization effect may be insufficient, whereas if the content of the phosphorus-based stabilizer exceeds the upper limit of the above range, the effect may plateau and become uneconomical.

[0083] Examples of the phenolic stabilizer include hindered phenolic antioxidants. Specific examples thereof include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6- triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, and the like.

[0084] Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred. Specific examples of such phenolic antioxidants include "Irganox 1010" and "Irganox 1076" manufactured by BASF, and "Adekastab AO-50" and "Adekastab AO-60" manufactured by ADEKA. The phenolic stabilizer may be contained in one kind or in any combination and ratio of two or more kinds.

[0085] The content of the phenolic stabilizer is preferably 0.01 parts by mass or more, and usually 1 part by mass or less, preferably 0.5 parts by mass or less, per 100 parts by mass of the polycarbonate resin (A). By setting the content of the phenolic stabilizer to the lower limit of the above range or more, the effect as a phenolic stabilizer can be sufficiently obtained. Furthermore, by setting the content of the phenolic stabilizer to the upper limit of the above range or less, the effect does not plateau and is economical.

[0086] [Elastomer] The polycarbonate resin composition of the present invention also preferably contains an elastomer. The elastomer is preferably a graft rubber copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith. Such a graft rubber copolymer may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., and the copolymerization method may be either single-stage grafting or multi-stage grafting.

[0087] The rubber component typically has a glass transition temperature of 0°C or lower, preferably -20°C or lower, and more preferably -30°C or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polyalkyl acrylate rubbers such as polybutyl acrylate, poly(2-ethylhexyl acrylate), and butyl acrylate-2-ethylhexyl acrylate copolymers, silicone rubbers such as organopolysiloxane rubber, butadiene-acrylic composite rubbers, IPN composite rubbers consisting of organopolysiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene rubber, ethylene-α-olefin rubbers such as ethylene-propylene rubber, ethylene-butene rubber, and ethylene-octene rubber, ethylene-acrylic rubber, and fluororubber. These may be used alone or in combination. Among these, polybutadiene rubber, polyalkyl acrylate rubber, IPN type composite rubber consisting of organopolysiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferred in terms of mechanical properties and surface appearance.

[0088] Specific examples of the monomer component graft-copolymerizable with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, (meth)acrylic acid compounds, epoxy group-containing (meth)acrylic acid ester compounds such as glycidyl (meth)acrylate; maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide; α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and their anhydrides (e.g., maleic anhydride). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, and (meth)acrylic acid compounds are preferred in terms of mechanical properties and surface appearance, and (meth)acrylic acid ester compounds are more preferred. Specific examples of (meth)acrylic acid ester compounds include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and octyl (meth)acrylate.

[0089] From the viewpoints of impact resistance and surface appearance, the elastomer is preferably a core / shell graft copolymer. Among these, a core / shell graft copolymer is preferred, which has a core layer made of at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, and an IPN-type composite rubber made of organopolysiloxane rubber and polyalkyl acrylate rubber, and a shell layer formed by copolymerizing a (meth)acrylic acid ester around the core. A core / shell graft copolymer with a butadiene-based rubber core is particularly preferred. The core / shell graft copolymer preferably contains 40% by mass or more of the rubber component, more preferably 60% by mass or more. Furthermore, the (meth)acrylic acid component is preferably 10% by mass or more.

[0090] Preferred specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber-styrene copolymer, methyl methacrylate-(acrylic-silicone IPN rubber) copolymer, etc. Such rubbery polymers may be used alone or in combination of two or more.

[0091] When the polycarbonate resin composition of the present invention contains the elastomer (D), it preferably contains the elastomer (D) in an amount of 0.01 to 10 parts by mass, particularly 1 to 10 parts by mass, and especially 2 to 8 parts by mass per 100 parts by mass of the polycarbonate resin (A).

[0092] [Release agent] The polycarbonate resin composition of the present invention preferably contains a release agent, such as an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000, or a polysiloxane-based silicone oil.

[0093] Examples of aliphatic carboxylic acids include saturated or unsaturated aliphatic mono-, di-, or tri-carboxylic acids. Aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are mono- or di-carboxylic acids having 6 to 36 carbon atoms, with saturated aliphatic mono-carboxylic acids having 6 to 36 carbon atoms being more preferred. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetralinic acid, montanic acid, adipic acid, and azelaic acid.

[0094] The aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol can be, for example, the same as the aliphatic carboxylic acid described above. On the other hand, the alcohol can be, for example, a saturated or unsaturated monohydric or polyhydric alcohol. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monohydric or polyhydric saturated alcohol having 30 or less carbon atoms is preferred, and an aliphatic saturated monohydric alcohol or an aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferred. Here, the term "aliphatic" is used to include alicyclic compounds.

[0095] Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, and dipentaerythritol.

[0096] The ester may contain an aliphatic carboxylic acid and / or an alcohol as an impurity. The ester may be a pure substance or a mixture of multiple compounds. The aliphatic carboxylic acid and the alcohol that combine to form an ester may each be used alone or in any combination and ratio of two or more.

[0097] Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

[0098] Examples of aliphatic hydrocarbons having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. Aliphatic hydrocarbons also include alicyclic hydrocarbons. These hydrocarbons may also be partially oxidized. Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferred, and paraffin wax and polyethylene wax are more preferred. The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less. The aliphatic hydrocarbon may be a single substance, but even if it is a mixture of substances with various constituent components and molecular weights, it is preferable that the main component is within the above range.

[0099] Examples of polysiloxane-based silicone oils include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone oil.

[0100] The above-mentioned release agents may be contained either alone or in any combination and ratio of two or more.

[0101] The content of the release agent is preferably 0.1 part by mass or more and preferably 1 part by mass or less, based on 100 parts by mass of the polycarbonate resin (A). By setting the content of the release agent to be equal to or more than the lower limit of the above range, sufficient release effect is easily obtained, and by setting the content of the release agent to be equal to or less than the upper limit of the above range, sufficient hydrolysis resistance is obtained and mold contamination during injection molding is less likely to occur.

[0102] [Other ingredients] The polycarbonate resin composition of the present invention may contain other components other than those described above, as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resins and various resin additives other than those described above. Note that one type of other component may be contained, or two or more types may be contained in any combination and ratio.

[0103] <Other resins> Other resins include, for example, thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate resin, and polybutylene terephthalate resin; styrene-based resins such as polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), and acrylonitrile-butadiene-styrene copolymer (ABS resin); polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; polyurethane resin; polyphenylene ether resin; polyphenylene sulfide resin; and polysulfone resin. The other resins may be contained either alone or in any combination and ratio of two or more. When other resins are contained, the amount thereof is preferably 30 parts by mass or less per 100 parts by mass of the polycarbonate resin (A), and more preferably 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, 7 parts by mass or less, 5 parts by mass or less, 3 parts by mass or less, and particularly preferably 1 part by mass or less.

[0104] <Resin additives> Examples of resin additives include ultraviolet absorbers, dyes and pigments (including titanium oxide and carbon black), antistatic agents, antifogging agents, antiblocking agents, plasticizers, dispersants, antibacterial agents, etc. One type of resin additive may be contained, or two or more types may be contained in any combination and ratio.

[0105] [Method for producing polycarbonate resin composition] There are no limitations on the method for producing the polycarbonate resin composition of the present invention, and a wide variety of known methods for producing polycarbonate resin compositions can be used, including a method in which the above-mentioned essential components and other components that are added as needed are premixed using various mixers such as a tumbler or a Henschel mixer, and then melt-kneaded using a mixer such as a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader, etc. When a twin-screw kneading extruder is used, it is preferable to side-feed the glass fiber. The melt-kneading temperature is not particularly limited, but is usually in the range of 240 to 320°C.

[0106] [Polycarbonate resin composition] The polycarbonate resin composition of the present invention has excellent thermal conductivity, and the thermal conductivity in the planar direction (resin flow direction) of a molded article of 100 mm × 100 mm × 3 mm conforming to ISO 22007-2 is preferably 0.7 W / mK or more, more preferably 0.8 W / mK or more, with the upper limit being preferably 3.0 W / mK or less. Specific methods for measuring thermal conductivity are as described in the Examples.

[0107] The polycarbonate resin composition of the present invention has excellent impact resistance, and the unnotched Charpy impact strength (4 mmt) measured in accordance with ISO 179 is preferably 20 kJ / m 2 More preferably, 25 kJ / m 2 The specific method for measuring the unnotched Charpy impact strength is as described in the Examples.

[0108] The polycarbonate resin composition of the present invention exhibits a low dielectric loss tangent, and the dielectric loss tangent measured at 2.45 GHz is preferably 0.007 or less, more preferably 0.006 or less. The lower limit of the dielectric loss tangent measured at 2.45 GHz may be 0.001 or more, and even 0.002 or more. Specific methods for measuring the dielectric loss tangent are as described in the Examples.

[0109] [Molded products] The polycarbonate resin composition is pelletized and then molded into molded articles by various molding methods. Alternatively, the resin can be melt-kneaded in an extruder and directly molded into molded articles without going through the pelletizing process. The shape of the molded article is not particularly limited and can be appropriately selected depending on the use and purpose of the molded article. Examples include a housing, a plate, a rod, a sheet, a film, a cylinder, an annular shape, a circle, an ellipse, a polygonal shape, an irregular shape, a hollow article, a frame, a box, a panel, and the like.

[0110] The method for molding the molded article is not particularly limited, and any conventionally known molding method can be used, such as injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, blow molding, gas-assisted blow molding, blow molding, extrusion blow molding, IMC (in-mold coating) molding, rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, pressure molding, etc. Of these, injection molding is particularly preferred.

[0111] The polycarbonate resin composition of the present invention is a resin material that is excellent in plating ability, thermal conductivity, and impact resistance and has a low dielectric dissipation factor, and therefore molded articles thereof are suitable for a variety of electric and electronic components, and are particularly suitable for, for example, components and housings for various mobile terminals, battery charging device components, battery covers, heat dissipation components and housings for projectors, heat dissipation components and housings for various routers and the like, components and housings for personal computers and digital cameras, LED mounting substrates or heat sink members and components for LED lighting, and the like. [Example]

[0112] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples and can be practiced with any modifications within the scope of the present invention. The raw material components used in the following Examples and Comparative Examples are as shown in Table 1 below.

[0113] [Table 1]

[0114] (Examples 1 to 8, Comparative Examples 1 to 7) The components shown in Table 1 above were blended in the proportions shown in Tables 2 and 3 below (all parts by mass), and the mixture was mixed uniformly in a tumbler mixer. The mixture was then fed into a twin-screw extruder (TEM26SX, manufactured by Shibaura Machine Co., Ltd.) from the upstream barrel at a cylinder temperature of 280°C, a screw rotation speed of 180 rpm, and a discharge rate of 15 kg / hr, and melt-kneaded to obtain pellets of a polycarbonate resin composition.

[0115] [Measurement of thermal conductivity (unit: W / m K)] The obtained pellets were injection molded into test pieces measuring 100 mm x 100 mm x 3 mmt using an injection molding machine (clamping force 80T) manufactured by Nissei Plastic Industrial Co., Ltd., under conditions of a cylinder temperature of 280°C and a mold temperature of 80°C. Using this test piece, the thermal conductivity (unit: W / m K) in the plane direction of the test piece (direction of resin flow) was measured using a hot disk method thermal property measuring device (Kyoto Electronics Manufacturing Co., Ltd., TPS-2500S) in accordance with ISO22007-2. The thermal conductivity is preferably 0.8 W / mK or more, and particularly preferably 1.0 W / mK or more.

[0116] [Evaluation of plating properties] The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours. Then, using a Nissei Plastic Industrial Co., Ltd. injection molding machine (clamping force 80T), a 100 x 100 mm, 2 mm thick cavity was filled with resin through a 100 mm x 1.5 mm thick fan gate at a cylinder temperature of 300°C and a mold temperature of 100°C. The gate was cut to obtain plate specimens. A 10 x 10 mm area of ​​the obtained plate specimen was irradiated using a Trumpf VMc1 laser irradiation device (1064 nm wavelength, YAG laser, maximum output 15 W) at a power of 6 W or 8 W, a frequency of 60 kHz or 80 kHz, and a speed of 2 m / s or 4 m / s. The subsequent plating process was performed in an electroless plating bath at 65°C using an Enthone ENPLATE LDS CU 400 PC. The plating performance within the above laser setting condition range was evaluated and judged according to the following four-level criteria. A: All plating is possible within the set conditions range, and the appearance is very good. B: Plating is possible under most of the set conditions and the appearance is good C: There are few plating conditions and the plating layer is thin D: Not plated

[0117] [Unnotched Charpy impact strength measurement] The resin composition pellets obtained above were dried at 120°C for 4 hours, and then injection molded using an injection molding machine (NEX80III type) manufactured by Nissei Plastic Industrial Co., Ltd. under the conditions of a cylinder setting temperature of 280°C, a mold temperature of 80°C, an injection time of 2 seconds, and a molding cycle of 50 seconds to injection mold an ISO multipurpose test piece (4 mm thick). Using the ISO multipurpose test piece (4mmt) obtained above, the unnotched Charpy impact strength (unit: kJ / m) was measured in accordance with ISO179-1 and ISO179-2. 2 ) was measured.

[0118] [Measurement of dielectric loss tangent] The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours, and then molded into molded articles measuring 100 mm x 100 mm and 2 mm thick using a fan gate mold using an injection molding machine NEX80III manufactured by Nissei Plastic Industrial Co., Ltd. Test pieces measuring 1 mm x 2 mm x 100 mm were prepared from the molded articles in the direction (parallel) to the resin flow direction. The dielectric loss tangent of the test piece at 2.45 GHz was measured using a cylindrical cavity resonator manufactured by Kanto Electronics Application Development Co., Ltd.

[0119] The results are shown in Tables 2 and 3 below.

[0120] [Table 2]

[0121] [Table 3] [Industrial Applicability]

[0122] The polycarbonate resin composition of the present invention is a resin material that is excellent in plating property, thermal conductivity, and impact resistance and has a low dielectric loss tangent, and therefore can be particularly suitably used for various electric and electronic equipment parts, etc.

Claims

1. A polycarbonate resin composition comprising, per 100 parts by mass of polycarbonate resin (A), 15 to 60 parts by mass of plate-like alumina (B), 15 to 60 parts by mass of a filler (C) other than (B), and 0.5 to 50 parts by mass of a laser direct structuring additive (D), wherein the mass ratio (C) / (B) of the other filler (C) to the plate-like alumina (B) is 0.5 or more, and further the mass ratio (B) / (D) of the plate-like alumina (B) to the laser direct structuring additive (D) is 6 or less.

2. 2. The polycarbonate resin composition according to claim 1, wherein the other filler (C) is talc.

3. 3. The polycarbonate resin composition according to claim 1, wherein the plate-like alumina (B) has an aspect ratio of 5 to 60.

4. 3. The polycarbonate composition according to claim 1, further comprising 0.5 to 10 parts by mass of a maleic anhydride olefin copolymer per 100 parts by mass of the polycarbonate resin (A).

5. 3. The polycarbonate composition according to claim 1, further comprising 0.01 to 10 parts by mass of an elastomer per 100 parts by mass of the polycarbonate resin (A).

6. 3. The polycarbonate resin composition according to claim 1, which is used for a thermally conductive molded product.

7. 3. The polycarbonate resin composition according to claim 1, which is for use in laser direct structuring molded articles.

8. 3. Pellets of the polycarbonate resin composition according to claim 1 or 2.

9. A molded article made from the polycarbonate resin composition according to claim 1 or 2.

10. A molded article comprising pellets of the polycarbonate resin composition according to claim 8.

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