Polycarbonate resin composition

Abstract

Provided is a polycarbonate resin composition which has excellent flame retardancy, excellent laser direct structuring performance, and excellent heat stability in residence and light-shielding properties, while being an environmentally friendly material that satisfies various regulations such as PFAS. This polycarbonate resin composition is characterised by containing, with respect to 100 parts by mass of a polycarbonate resin (A) containing 10-80 mass% of an aromatic polycarbonate resin (A1) having a viscosity average molecular weight of 50,000 to 90,000; 0.5 to 50 parts by mass of a laser direct structuring additive (B); 0.01 to 1 parts by mass of an organic sulfonic acid metal salt (C); and 0.1 to 2.5 parts by mass of a flame retardant auxiliary (D) having no phosphorus or halogens.

Description

Polycarbonate resin composition

[0001] The present invention relates to a polycarbonate resin composition, and more specifically, to a polycarbonate resin composition that meets various regulations such as PFAS and is environmentally friendly, while possessing excellent flame retardancy, superior laser direct structuring performance, and excellent heat retention stability and light shielding properties.

[0002] Polycarbonate resin is a resin with excellent heat resistance, mechanical properties, and electrical properties, and is widely used as a material for manufacturing parts in various industrial fields, such as vehicle parts, electrical and electronic equipment components, housing materials, and other industrial sectors. In particular, flame-retardant polycarbonate resin compositions are suitably used as parts for vehicle parts, electrical and electronic equipment components such as personal computers, mobile phones, and battery cases, and components for office automation and information equipment such as printers and photocopiers.

[0003] In recent years, there has been a growing demand for methods to manufacture antennas capable of 3D design for a wide range of applications, including smartphones, various 5G devices, in-vehicle communication systems, and base stations. One such technology for forming 3D antennas is laser direct structuring (hereinafter sometimes referred to as "LDS"), which has attracted considerable attention. LDS technology is a technique in which, for example, a laser is irradiated onto the surface of a molded product (resin molded product) containing an LDS additive to activate it, and a plating layer is formed by applying metal to the activated portion. The characteristic of this technology is that metal structures such as antennas can be manufactured directly on the surface of a resin molded product without using adhesives or the like (for example, Patent Document 1).

[0004] In recent years, there has been a growing demand for flame retardancy, and polycarbonate resin molded products are now required to have a high degree of flame retardancy. This demand is increasingly for extremely high flame retardancy, such as achieving V-0 in UL-94 testing even with a thin wall thickness of 1.5 mm. Halogen-based and phosphorus-based flame retardants have been used to impart flame retardancy to polycarbonate resins. However, achieving V-0 flame retardancy with phosphorus-based flame retardants requires a relatively high additive rate, which tends to degrade the mechanical properties of the polycarbonate resin material. Flame retardation using halogen-based bromine-based or chlorine-based flame retardants is facing stricter regulations due to toxicity and environmental problems caused by the generation of harmful gases. Fluorine-based flame retardants, such as perfluoroalkane metal salts, enable high levels of flame retardancy with relatively small amounts. Furthermore, by combining such flame retardants with polyfluoroethylene as a drip-preventing agent, dripping can be suppressed, further improving flame retardancy. However, in recent years, fluorine compounds have become subject to international regulations, primarily in Japan, Europe, and the United States. PFAS regulations for perfluoroalkyl and polyfluoroalkyl compounds are progressing, mainly in the EU and the US, and polyfluoroethylenes are also included. PFAS regulations are being further strengthened internationally.

[0005] International Publication No. 2009 / 141799

[0006] Therefore, there is a strong demand for a highly functional, flame-retardant polycarbonate resin composition for LDS that does not generate toxic gases during combustion, clears various regulations, and is environmentally friendly. Furthermore, recently, there is a need for excellent appearance of molded products after stagnation molding, and for antenna components formed on the surface of resin molded products by LDS, light shielding properties are required from the viewpoint of design and confidentiality. The present invention has been made in view of the above circumstances, and its objective (problem) is to provide a polycarbonate resin composition that is environmentally friendly, clears various regulations such as PFAS, has excellent flame retardancy, has excellent laser direct structuring performance, and has excellent stagnation thermal stability and light shielding properties.

[0007] The inventors, after diligent research to achieve the above objectives, discovered that the above objectives can be solved by combining a polycarbonate resin containing a specific amount of aromatic polycarbonate resin with a viscosity-average molecular weight of 50,000 to 90,000 with an LDS additive, an organic sulfonic acid metal salt, and a flame retardant additive that does not contain phosphorus or halogens, each in specific amounts. This led to the completion of the present invention. The present invention relates to the following polycarbonate resin composition and molded article.

[0008] 1. A polycarbonate resin composition characterized by containing 10 to 80% by mass of an aromatic polycarbonate resin (A1) having a viscosity-average molecular weight of 50,000 to 90,000, with 0.5 to 50 parts by mass of a laser direct structuring additive (B), 0.01 to 1 part by mass of an organic sulfonic acid metal salt (C), and 0.1 to 2.5 parts by mass of a flame retardant additive (D) that does not contain phosphorus or halogen, per 100 parts by mass of polycarbonate resin (A) having an viscosity-average molecular weight of 50,000 to 90,000. 2. 1. A polycarbonate resin composition according to 1, comprising 100 parts by mass of polycarbonate resin (A) containing 10 to 80% by mass of linear aromatic polycarbonate resin (A1) having a viscosity-average molecular weight of 50,000 to 90,000, 0.5 to 50 parts by mass of laser direct structuring additive (B), 0.01 to 1 part by mass of organic sulfonic acid metal salt (C), and 0.1 to 2.5 parts by mass of a flame retardant aid (D) that does not contain phosphorus or halogen. 3. A polycarbonate resin composition according to 1 or 2, wherein the fluorine content measured by combustion ion chromatography is less than 500 ppm by mass. 4. A polycarbonate resin composition according to any one of 1 to 3, wherein the organic sulfonic acid metal salt (C) is an aromatic sulfonic acid metal salt. 5. 1. A polycarbonate resin composition according to any one of 1 to 4 above, wherein the flame retardant additive (D) that does not contain phosphorus or halogen is one or more of the following: a mineral containing aluminum or magnesium, or a silicone-based flame retardant additive. 6. A polycarbonate resin composition according to any one of 1 to 5 above, wherein the UL-94 of a 1.5 mm thick film is V-0. 7. A polycarbonate resin composition according to any one of 1 to 6 above, wherein the spectral transmittance at a wavelength of 700 nm in the thickness direction, measured on a 50 μm thick film molded from the polycarbonate resin composition, is less than 20%. 8. A polycarbonate resin composition according to any one of 1 to 7 above for use in laser direct structuring molded articles. 9. Pellets of the polycarbonate resin composition according to any one of 1 to 8 above. 10. A molded article made from the polycarbonate resin composition according to any one of 1 to 8 above. 11. A molded article made from pellets of the polycarbonate resin composition according to 9 above.

[0009] The polycarbonate resin composition of the present invention is an environmentally friendly material that clears various regulations such as PFAS, does not generate toxic gases when burned, has high flame retardancy that is environmentally friendly, can achieve V-0 at a thickness of 1.5 mm, has excellent LDS performance, has excellent heat retention stability, and also has excellent design and light shielding properties.

[0010] The present invention will be described in detail below with reference to embodiments and examples. In this specification, unless otherwise specified, "~" means that the numerical values ​​described before and after it are included as the lower limit and upper limit.

[0011] The polycarbonate resin composition of the present invention is characterized by containing, in proportion to 100 parts by mass of polycarbonate resin (A) containing 10 to 80% by mass of aromatic polycarbonate resin (A1) having a viscosity-average molecular weight of 50,000 to 90,000, 0.5 to 50 parts by mass of laser direct structuring additive (B), 0.01 to 1 part by mass of organic sulfonic acid metal salt (C), and 0.1 to 2.5 parts by mass of a flame retardant aid (D) that does not contain phosphorus or halogen.

[0012] [Polycarbonate Resin (A)] The polycarbonate resin (A), which is component (A) of the present invention, contains an aromatic polycarbonate resin (A1) having a viscosity-average molecular weight of 50,000 to 90,000. The viscosity-average molecular weight (Mv) of the polycarbonate resin (A1) is preferably 55,000 or more, more preferably 57,000 or more, more preferably 59,000 or more, particularly preferably 60,000 or more, and also preferably 88,000 or less, particularly preferably 86,000 or less, 85,000 or less, 83,000 or less, 82,000 or less, 81,000 or less, and particularly preferably 80,000 or less. The polycarbonate resin (A1) may be one type, or two or more types of polycarbonate resins may be mixed and used. When two or more types are mixed and used, it is preferable to mix polycarbonate resins whose Mv is within the above range.

[0013] The amount of aromatic polycarbonate resin (A1) having a viscosity-average molecular weight of 50,000 to 90,000 in polycarbonate resin (A) is 10 to 80% by mass, preferably 11% by mass or more, more preferably 12% by mass or more, particularly preferably 13% by mass or more, preferably 75% by mass or less, more preferably 70% by mass or less, and particularly preferably 68% by mass or less.

[0014] In this invention, the viscosity-average molecular weight (Mv) of the polycarbonate resin is determined by using methylene chloride as the solvent, and calculating the intrinsic viscosity [η] (unit dl / g) at a temperature of 25°C using an Ubbelohde viscometer, and then using Schnell's viscosity formula, i.e., η = 1.23 × 10⁻¹⁰ －４ Mv ０．８３ It refers to the value calculated from [the formula]. Furthermore, intrinsic viscosity [η] is the specific viscosity [η] at each solution concentration [C] (g / dl). ｓｐ This value is calculated by measuring [the value] and using the following formula.

[0015] The aromatic polycarbonate resin (A1) may be linear or branched, as long as its viscosity-average molecular weight (Mv) is within the above range. A mixture of two or more linear and branched polycarbonate resins can also be used, but linear is particularly preferred. In the present invention, a linear aromatic polycarbonate resin refers to one that does not substantially have a branched structure in the polycarbonate resin main chain, and a polycarbonate resin obtained by interfacial polymerization of an aromatic dihydroxy compound and carbonyl chloride is preferred. A branched aromatic polycarbonate resin refers to one that has a branched structure in the polycarbonate main chain, and examples include those obtained using a branching agent, or polycarbonate resins obtained without using a branching agent by selecting catalyst conditions or manufacturing conditions when reacting a dihydroxy compound with a diester of carbonic acid by melt transesterification.

[0016] Component (A) of the polycarbonate resin of the present invention, the polycarbonate resin (A), contains other polycarbonate resins (A2) other than the aromatic polycarbonate resin (A1) having a viscosity average molecular weight of 50,000 to 90,000 described above. As the other polycarbonate resin (A2), preferably a linear or branched aromatic polycarbonate resin having a viscosity average molecular weight of less than 50,000, more preferably 10,000 or more to less than 50,000, still more preferably 11,000 to 40,000, especially 12,000 to 35,000, particularly 13,000 to 30,000 is preferred. The polycarbonate resin (A) of the present invention combines a high molecular weight aromatic polycarbonate resin (A1) in the above-described amount with other polycarbonate resins (A2), thereby making it possible to improve the flame retardancy, retention heat stability and fluidity of the resin composition.

[0017] The polycarbonate resin (A2) used in the present invention is preferably an aromatic polycarbonate resin from the viewpoints of heat resistance, mechanical properties, electrical properties, etc.

[0018] The aromatic polycarbonate resin is an aromatic polycarbonate resin in which the carbon directly bonded to the carbonate bond is each an aromatic carbon. Among the monomers that are raw materials for the aromatic polycarbonate resins (A1) and (A2), examples of aromatic dihydroxy compounds include dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (i.e., resorcinol), 1,4-dihydroxybenzene; dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl;

[0019] 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, 2,7-dihydroxynaphthalene;

[0020] 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;

[0021] 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, Bis(hydroxyaryl)alkanes such as 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)nonane, 1,1-bis(4-hydroxyphenyl)decane, and 1,1-bis(4-hydroxyphenyl)dodecane;

[0022] 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, and other bis(hydroxyaryl)cycloalkanes;

[0023] 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and other bisphenols containing a cardo structure;

[0024] 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, and other dihydroxydiaryl sulfides; 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, and other dihydroxydiaryl sulfoxides; 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, and other dihydroxydiaryl sulfones; and the like.

[0025] Among these, bis(hydroxyaryl)alkanes are preferred, and among them, bis(4-hydroxyphenyl)alkanes are preferred, and in particular, 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 from the viewpoint of impact resistance and heat resistance. Note that one aromatic dihydroxy compound may be used, or two or more may be used in any combination and ratio.

[0026] Among the monomers used as raw materials for polycarbonate resin, examples of carbonate precursors include carbonyl halides and carbonate esters. Note that one type of carbonate precursor may be used, or two or more types may be used in any combination and ratio.

[0027] Examples of carbonyl halides include, specifically, phosgene; and haloformates such as bischloroformates and monochloroformates of dihydroxy compounds.

[0028] Examples of carbonate esters include diaryl carbonates such as diphenyl carbonate and dityl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; and carbonates of dihydroxy compounds such as biscarbonates, monocarbonates, and cyclic carbonates of dihydroxy compounds.

[0029] Furthermore, the polycarbonate resin (A) may be made not only from virgin raw materials but also from polycarbonate resin recycled from used products (so-called material-recycled polycarbonate resin), and it is also preferable to contain both virgin raw materials and recycled resin, or to consist solely of recycled polycarbonate resin. The proportion of recycled polycarbonate resin in the polycarbonate resin (A) is preferably 30% or more, and more preferably 40% or more, 50% or more, 60% or more, 70% or more, or 80% or more, and it is also preferable for the recycled polycarbonate resin to be 100%.

[0030] [LDS Additive (B)] The polycarbonate resin composition of the present invention contains a laser direct structuring (LDS) additive (B). When the LDS additive is irradiated with a laser beam, metal atoms are activated and a metal layer is formed on the surface.

[0031] As an LDS additive (B), copper chromium oxide (CuCr ２ O ４ Examples of preferred materials include heavy metal composite oxides such as spinel; copper salts such as copper hydroxide phosphate, copper phosphate, copper sulfate, and copper thiocyanate; antimony-containing tin oxides such as antimony-doped tin oxide; and aluminum-doped zinc oxide. Of these, copper-chromium oxide or antimony-containing tin oxide are more preferred. Furthermore, copper-chromium oxide also functions as a black pigment, making it suitable for obtaining black molded products, and antimony-containing tin oxide can be used as a white pigment, so it can be applied as a white molded product, or in combination with other colored pigments to create desired color variations.

[0032] The particle size of the LDS additive (B) is preferably 0.01 to 50 μm, and more preferably 0.05 to 30 μm. This particle size tends to result in better uniformity of the plated surface when plating is applied.

[0033] The content of the LDS additive (B) is 0.5 to 50 parts by mass per 100 parts by mass of polycarbonate resin (A), preferably 1 part by mass or more, more preferably 3 parts by mass or more, particularly preferably 5 parts by mass or more, and also preferably 45 parts by mass or less, more preferably 40 parts by mass or less, 35 parts by mass or less, 30 parts by mass or less, 25 parts by mass or less, particularly preferably 20 parts by mass or less.

[0034] A molded product formed by injection molding or the like using a polycarbonate resin composition containing LDS additive (B) can be plated by irradiating its surface with a laser beam. For example, by irradiating a laser beam in a desired pattern, such as the antenna circuit of a mobile device, an activated metal layer is formed only in the area where the circuit pattern is to be formed on the surface of the molded product, and a surface structure advantageous for subsequent metal plating is created. The molded product is then immersed in a plating solution and plated with copper, nickel, gold, etc., by electroplating (or electroplating) to form the circuit pattern.

[0035] In recent years, there has been a growing trend towards more flexible design for antenna components in mobile devices. This has led to a need to control the appearance of antenna components through methods such as LIM molding and two-color molding. From the standpoint of aesthetics or confidentiality, antenna components are sometimes required to have light-shielding properties, and the polycarbonate resin composition of the present invention also exhibits excellent light-shielding effects, as shown in the examples described later.

[0036] [Organosulfonic Acid Metal Salt (C)] The polycarbonate resin composition of the present invention contains an organic sulfonic acid metal salt (C). As the organic sulfonic acid metal salt (C), a non-phosphorus, non-halogen organic sulfonic acid metal salt flame retardant that does not contain phosphorus and / or halogens in its molecule is preferred.

[0037] The metal in the metal salt is preferably an alkali metal or an alkaline earth metal, such as alkali metals like lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs); and alkaline earth metals like magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). Among these, sodium, potassium, and cesium are preferred, with sodium and potassium being particularly preferred.

[0038] Preferred examples of the organic sulfonic acid metal salt (C) include metal salts of aromatic sulfonic acids, metal salts of aromatic sulfonamides (or sulfonimides), and metal salts of polystyrene sulfonic acid.

[0039] Specific examples of these include alkali metal salts of aromatic sulfonic acids having at least one aromatic group in their molecule, such as potassium 3-(phenylsulfonyl)benzenesulfonate (i.e., potassium diphenylsulfon-3-sulfonate), dipotassium diphenylsulfon-3,3'-disulfonate, sodium benzenesulfonate, potassium benzenesulfonate, cesium benzenesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, cesium p-toluenesulfonate, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, cesium dodecylbenzenesulfonate, potassium styrenesulfonate, sodium polystyrenesulfonate, potassium polystyrenesulfonate, and cesium polystyrenesulfonate; and alkaline earth metal salts of aromatic sulfonic acids having at least one aromatic group in their molecule, such as magnesium p-toluenesulfonate, calcium p-toluenesulfonate, strontium p-toluenesulfonate, barium p-toluenesulfonate, magnesium dodecylbenzenesulfonate, and calcium dodecylbenzenesulfonate.

[0040] Examples of metal salts of aromatic sulfonamides (or sulfonimides) include potassium salt of N-(p-tolylsulfonyl)-p-toluenesulfoimide, potassium salt of N-(N'-benzylaminocarbonyl)sulfanilimide, and potassium salt of N-(phenylcarboxyl)-sulfanilimide.

[0041] Among the above, metal salts of p-toluenesulfonic acid, phenylsulfonylbenzenesulfonic acid, and polystyrenesulfonic acid are preferred as the organic sulfonic acid metal salt (C), and among these, alkali metal salts, especially sodium salts or potassium salts, are preferred. One type of organic sulfonic acid metal salt (C) may be used alone, or two or more types may be used in any combination and ratio.

[0042] The content of the organic sulfonic acid metal salt (C) is 0.01 to 1 part by mass per 100 parts by mass of polycarbonate resin (A), preferably 0.02 parts by mass or more, more preferably 0.03 parts by mass or more, 0.05 parts by mass or more, 0.08 parts by mass or more, or 0.1 parts by mass or more, and more preferably less than 1.0 part by mass, more preferably 0.7 parts by mass or less, 0.5 parts by mass or less, and especially preferably 0.4 parts by mass or less.

[0043] It is preferable that the polycarbonate resin composition of the present invention substantially does not contain phosphorus-based flame retardants and / or halogen-based flame retardants. Here, "substantially contained" means that the amount of phosphorus-based flame retardants and / or halogen-based flame retardants, individually or in total, is preferably less than 0.05 parts by mass, more preferably less than 0.03 parts by mass, more preferably less than 0.01 parts by mass, less than 0.005 parts by mass, less than 0.001 parts by mass, and particularly preferably less than 0.0005 parts by mass, per 100 parts by mass of polycarbonate resin (A).

[0044] [Flame retardant additive (D) that does not contain phosphorus or halogen] The polycarbonate resin composition of the present invention contains a flame retardant additive (D) that does not contain phosphorus or halogen. A flame retardant additive is one that, when used in combination with an organic sulfonic acid metal salt (C) used to make polycarbonate resin flame retardant, exhibits a synergistic effect.

[0045] Preferred examples of flame retardant additive (D) include minerals containing intercalated water and / or structural water, or silicone-based flame retardant additives.

[0046] Minerals containing interlayer water and / or structural water release interlayer water and structural water when exposed to high heat such as flames, and the resulting cooling and diluting effect dehydrates them, further improving the flame retardancy of organic sulfonic acid metal salts (C). Preferred such minerals include those containing aluminum or magnesium, such as boehmite, halloysite, sepiolite, hydromagnesite, kaolin, montmorillonite, pyrophyllite, attapulgite, and vermiculite. These minerals release structural water before the polycarbonate resin completely decomposes during combustion, exhibiting a flame retardant effect.

[0047] Boehmite is a monohydrate alumina represented by the compositional formula: Al ２ O ３ ・1H ２ O, and is preferred because it has particularly high heat resistance and chemical stability. Halloysite is a type of clay mineral classified as a phyllosilicate mineral. Typically, its chemical formula is Al ２ Si ２ O ５ (OH ４ ). Halloysite has a layered structure with weak bonds between unit layers and water molecules incorporated between the layers, and has a roll-shaped tubular form. The mechanism by which halloysite exhibits flame retardancy as a flame retardant aid is that when exposed to high heat such as a flame, interlayer water and structural water are released, and due to its cooling and dilution effects, also, the aluminol surface (-Al-OH ＋ ) inside halloysite becomes an acid site, suppressing the formation of low molecular weight components by the cleavage reaction of the polycarbonate resin and facilitating the formation of a crosslinked structure by an isomerization reaction, thereby promoting good char formation. Sepiolite is a type of clay mineral classified as a phyllosilicate mineral. Typically, its chemical formula is Mg ８ Si １２ O ３０ (OH ４ (OH ２ ) ４ ・8H ２ O. Sepiolite is a fibrous mineral composed of discontinuous layers, is porous and has a large specific surface area, and is characterized by high adsorptivity for water and the like. The mechanism by which sepiolite exhibits flame retardancy is thought to be that when exposed to high heat such as a flame, interlayer water and structural water are released, resulting in a cooling and dilution effect, and the fibrous structure of sepiolite reinforces the formed char.

[0048] Hydrotalcite is a hydrated basic carbonate mineral of magnesium, and typically is a mineral represented by Mg ５ (CO ３ ) ４ (OH ２ ・4H ２ O. Kaolin, also called kaolinite and kaolin stone, typically has the formula Al ２ Si ２ O５ (OH) ４ It is a mineral represented by [this symbol]. Montmorillonite is a type of silicate mineral, typically (Na,Ca) ０．３３ (Al, Mg) ２ Si ４ O １０ (OH) ２ nH ２ It is represented by O. Pyrophyllite is a type of layered silicate mineral, typically Al ２ Si ４ O １０ (OH) ２ It is represented as [Mg(Al]. Attapulgite is a natural silicate mineral whose main components are hydrated magnesium and aluminum silicate, and is typically represented as [Mg(Al]. （０．５－１） Fe （０－０．５） ) ] Si ４ O １０ (OH) 4H ２ It is represented by O. Vermiculite is a type of silicate mineral formed from weathered biotite and phlogopite, and its chemical composition is Mg １－ｘ (Mg, Fe, Fe ３＋ ,Al) ３ (Si, Al) ４ O １０ (OH) ２ 4H ２ It is represented by O.

[0049] The above-mentioned mineral-based flame retardant additives release interlayer water and / or structural water, and through their cooling and diluting effects, and by promoting the formation of strong char by the organic sulfonic acid metal salt (C), they achieve extremely good flame retardancy, allowing the material to meet regulations such as PFAS and be environmentally friendly.

[0050] The above-mentioned mineral-based flame retardant additives are preferably surface-treated. Specific examples of surface treatment agents include silicone compounds such as organopolysiloxanes, coupling agents such as silane-based coupling agents, titanate-based coupling agents, and aluminum-based coupling agents, alcohols such as trimethylolethane, trimethylolpropane, and pentaerythritol, alkanolamines such as triethylamine, higher fatty acids such as stearic acid, fatty acid metal salts such as calcium stearate and magnesium stearate, polyacrylates such as sodium polyacrylate and ammonium polyacrylate, hydrocarbon lubricants such as polyethylene wax and liquid paraffin, basic amino acids such as lysine and arginine, polyglycerin, and their derivatives. Among these, silicone compounds such as organopolysiloxanes are preferred because surface treatment with silicone compounds improves heat resistance and dispersibility in polycarbonate resins, resulting in a significant improvement in flame retardancy.

[0051] Polyorganosiloxanes are preferred as silicone-based flame retardants. Among these, polyorganosiloxanes having aromatic groups such as phenyl groups in their molecules are preferred. Examples of such polyorganosiloxanes include polydiphenylsiloxane, polymethylphenylsiloxane, polydimethyldiphenylsiloxane, and phenyl group-containing cyclic siloxanes.

[0052] Furthermore, polyorganosiloxanes may contain functional groups such as silanol groups, epoxy groups, alkoxy groups, hydrosilyl (SiH) groups, and vinyl groups in addition to the organic groups mentioned above. The inclusion of these special functional groups can improve the compatibility between the polyorganosiloxane and the polycarbonate resin, and enhance its reactivity during combustion, thereby increasing its flame retardancy.

[0053] The silanol group content in polyorganosiloxane is typically 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more, and typically 10% by mass or less, preferably 9% by mass or less, more preferably 8% by mass or less, and particularly preferably 7.5% by mass or less. A high flame retardant effect tends to be obtained by keeping the silanol group content within the above range, and if the silanol group content is too high, the thermal stability of the polycarbonate resin composition may be significantly reduced.

[0054] Furthermore, polyorganosiloxanes may contain alkoxy groups in addition to hydroxyl groups, but it is preferable that the amount of alkoxy groups be 10% by mass or less. This is because if the amount of alkoxy groups exceeds 10% by mass, gelation is more likely to occur, which may lead to a decrease in the mechanical properties of the polycarbonate resin composition.

[0055] Furthermore, the silicone-based flame retardant additive is preferably a graft copolymer containing a polyorganosiloxane. It may also be a modified polyorganosiloxane containing the above-mentioned polyorganosiloxane graft copolymerized with other (co)polymers, such as butyl polyacrylate or butyl acrylate-styrene copolymer.

[0056] Silicone-based flame retardants may be used individually or in mixtures of two or more types.

[0057] The properties of the silicone-based flame retardant additive are not limited to solid or liquid form, but a melting point of 50°C or higher is preferable in that it forms a strong foamed char. The melting point is more preferably 60°C or higher, and even more preferably 70°C or higher.

[0058] The content of the flame retardant additive (D) is 0.1 to 2.5 parts by mass per 100 parts by mass of polycarbonate resin (A), and good flame retardancy is achieved with such a small content. Below the lower limit, the flame retardancy is insufficient, and if the amount exceeds the upper limit, the decomposition of the polycarbonate progresses and it is difficult to achieve good flame retardancy. The content of the flame retardant additive (D) is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and more preferably 2.3 parts by mass or less per 100 parts by mass of polycarbonate resin (A), with particularly preferred amounts being 2.0 parts by mass or less, 1.8 parts by mass or less, 1.5 parts by mass or less, 1.3 parts by mass or less, 1.1 parts by mass or less, 1.0 part by mass or less, less than 1.0 part by mass, 0.9 parts by mass or less, 0.8 parts by mass or less, and especially less than 0.8 parts by mass.

[0059] [Release Agent] The resin composition of the present invention preferably contains a release agent. Examples of release agents include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number average molecular weight of 200 to 15,000, and polysiloxane-based silicone oils.

[0060] Examples of aliphatic carboxylic acids include saturated or unsaturated aliphatic monovalent, divalent, or trivalent carboxylic acids. Here, aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and more preferably aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetrariacontanoic acid, montanic acid, adipic acid, and azelaic acid.

[0061] As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, for example, the same aliphatic carboxylic acid as described above can be used. On the other hand, as the alcohol, for example, saturated or unsaturated monohydric or polyhydric alcohols can be used. These alcohols may have substituents such as fluorine atoms or aryl groups. Among these, monohydric or polyhydric saturated alcohols having 30 or fewer carbon atoms are preferred, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or fewer carbon atoms are more preferred. Here, "aliphatic" is used as a term that also includes alicyclic compounds.

[0062] 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.

[0063] Furthermore, the above-mentioned esters may contain aliphatic carboxylic acids and / or alcohols as impurities. Also, the above-mentioned esters may be pure substances or mixtures of multiple compounds. Moreover, the aliphatic carboxylic acids and alcohols that combine to form a single ester may be used individually, or two or more may be used in any combination and ratio.

[0064] Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture mainly composed of myricyl palmitate), 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.

[0065] Examples of aliphatic hydrocarbons with a number-average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. Alicyclic hydrocarbons are also included as aliphatic hydrocarbons. These hydrocarbons may also be partially oxidized. Among these, paraffin wax, polyethylene wax, or partially oxidized polyethylene wax are preferred, with paraffin wax and polyethylene wax being more preferred. The number-average molecular weight of the aliphatic hydrocarbons is preferably 5,000 or less. The aliphatic hydrocarbon may be a single substance, but a mixture of substances with various components and molecular weights can also be used as long as the main component is within the above range.

[0066] Examples of polysiloxane-based silicone oils include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

[0067] Furthermore, the mold release agent described above may contain one type, or two or more types in any combination and ratio.

[0068] The release agent content is preferably 0.1 to 2 parts by mass, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less, per 100 parts by mass of polycarbonate resin (A). If the release agent content is below the lower limit of the above range, the release effect is likely to be insufficient, and if it exceeds the upper limit of the above range, a decrease in hydrolysis resistance and mold contamination during injection molding may occur.

[0069] [Stabilizer] The polycarbonate resin composition of the present invention preferably contains a stabilizer, and phosphorus-based stabilizers or phenol-based stabilizers are preferred.

[0070] Any known phosphorus-based stabilizer can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphate; acidic pyrophosphate metal salts such as sodium acidic pyrophosphate, potassium acidic pyrophosphate, and calcium acidic pyrophosphate; phosphates of Group 1 or Group 2 metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; and organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds, with organic phosphate compounds and organic phosphite compounds being particularly preferred.

[0071] Examples of organic phosphate compounds include octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, octadecyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, and bisphenol. Examples of such organic phosphate compounds include hydroxya-1 acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, bisnonylphenyl acid phosphate, etc., or their metal salts. Examples of such organic phosphate compounds include "ADEKA AX-71" manufactured by ADEKA Corporation and "JP-518Zn" manufactured by Johoku Chemical Industry Co., Ltd.

[0072] 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, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite, distearylpentaerythritol diphosphite, and bis(2,4-dicumylphenyl)pentaerythritol phosphite. Examples of such organic phosphite compounds include "ADEKA Stab 1178," "ADEKA Stab 2112," "ADEKA Stab HP-10," "ADEKA Stab PEP-36," and "ADEKA Stab PEP-8" from ADEKA Corporation, "JP-351," "JP-360," and "JP-3CP" from Johoku Chemical Industry Co., Ltd., and "Irgaphos 168" from BASF. Note that the phosphorus stabilizer may contain one type, or two or more types in any combination and ratio.

[0073] The phosphorus-based stabilizer content is typically 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, per 100 parts by mass of polycarbonate resin (A), and typically 1 part by mass or less, preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass or less. If the phosphorus-based stabilizer content is below the lower limit of the above range, the thermal stabilization effect may be insufficient, and if the phosphorus-based stabilizer content exceeds the upper limit of the above range, the effect may plateau and become uneconomical.

[0074] Examples of phenolic stabilizers include hindered phenolic antioxidants. Specific examples 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- Examples include triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[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-triazine-2-ylamino)phenol, and 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate.

[0075] 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, for example, BASF's "Irganox 1010" and "Irganox 1076," and ADEKA's "ADEKA Stab AO-50" and "ADEKA Stab AO-60." Note that the phenolic stabilizer may contain only one type, or two or more types in any combination and ratio.

[0076] The content of the phenolic stabilizer is usually 0.001 parts by mass or more, 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 polycarbonate resin (A). By setting the content of the phenolic stabilizer above the lower limit of the above range, the effect of the phenolic stabilizer can be sufficiently obtained, and by setting it below the upper limit of the above range, the effect does not plateau, making it economical. It is preferable to include both the phosphorus-based stabilizer and the phenolic stabilizer, as this further improves stability.

[0077] [Additives, etc.] The polycarbonate resin composition of the present invention may contain other additives besides those mentioned above, such as fillers, ultraviolet absorbers, fluorescent whitening agents, pigments, dyes, plasticizers, and compatibilizers. These additives may be present in one or more types.

[0078] Furthermore, other resins besides polycarbonate resin (A) may be included. Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate; styrene-based resins such as polystyrene resin, high-impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS 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; polysulfone resin; and polymethacrylate resin. When other resins besides polycarbonate resin (A) are included, the content is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and more preferably 20 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, and especially preferably 1 part by mass or less, per 100 parts by mass of polycarbonate resin (A).

[0079] [Polycarbonate Resin Composition] The polycarbonate resin composition of the present invention has high flame retardancy and can achieve V-0 in the UL-94 test with a UL test piece that is 1.5 mm thick. Furthermore, the polycarbonate resin composition of the present invention has excellent light shielding properties, and the spectral transmittance at a wavelength of 700 nm in the thickness direction, measured on a 50 μm thick film molded from the polycarbonate resin composition, is preferably less than 20%. Even with a thin thickness of 50 μm, and at a wavelength of 700 nm which is considered to have high transmittance among visible light, a high level of light shielding with a transmittance of less than 20% can be achieved.

[0080] The polycarbonate resin composition of the present invention is molded into a molded article. The method for manufacturing the molded article can be any molding method that is generally used for polycarbonate resin compositions. Examples include injection molding, ultra-high-speed injection molding, injection compression molding, two-color molding, hollow molding methods such as gas-assisted molding, molding using a heat-insulating mold, molding using a rapidly heated mold, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating) molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding, blow molding, etc. Molding methods using a hot runner system can also be used. Among these, injection molding methods such as injection molding, ultra-high-speed injection molding, and injection compression molding are preferred.

[0081] [Molded Products] Examples of molded products include electrical and electronic equipment, office automation equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building materials, various containers, leisure goods and miscellaneous items, and lighting equipment components. In particular, they are suitable for use in electrical and electronic equipment, office automation equipment, information terminal equipment, home appliances, and lighting equipment components. For example, they are suitable for use in components for secondary battery devices used indoors or outdoors, battery packs, storage batteries for electric bicycles, and components for enclosures used outdoors.

[0082] A plating can be formed on the surface of a resin molded product by laser direct structuring. The shape of the resin molded product can be anything; it can be flat, partially or entirely curved, or have a complex three-dimensional shape. The resin molded product is irradiated with a laser, but there are no particular limitations on the laser; it can be appropriately selected from known lasers such as YAG lasers, FAYb lasers, carbon dioxide lasers, and excimer lasers, with YAG lasers and FAYb lasers being preferred. The wavelength of the laser is also not particularly specified. A preferred wavelength range is 200 nm to 1200 nm, and particularly preferred is 800 nm to 1200 nm. When the laser is irradiated, an activated metal layer is formed only in the irradiated area on the surface of the molded product, and surface roughening advantageous for subsequent metal plating is achieved. The molded product is immersed in a plating solution with or without a cleaning step, and plated with copper, nickel, gold, silver, palladium, preferably copper, by electroplating (or electroplating), and a metal layer is formed only in the laser-irradiated area.

[0083] Furthermore, by applying laser direct structuring to the molded product of the present invention, it is possible to form circuits with a width of, for example, 1 mm or less, and even 150 μm or less (the lower limit is not specifically defined, but for example, 30 μm or more). Therefore, it is extremely effective for various mobile devices such as smartphones and tablet terminals, hearing aids, medical or dental treatment and surgical devices, various sensors, automotive devices such as steering wheel switches, or their components.

[0084] As mentioned above, in recent years, there has been a demand to conceal the formed antenna patterns, etc., from the standpoint of design or confidentiality, and the molded articles of the polycarbonate resin composition of the present invention also have excellent light-shielding properties.

[0085] 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. The components used in the examples and comparative examples are shown in Table 1 below.

[0086]

[0087] (Examples 1-12, Comparative Examples 1-12) <Production of Resin Composition Pellets> The above components were blended in the proportions (parts by mass) shown in Table 2-3 below, mixed in a tumbler for 20 minutes, and then supplied to a twin-screw extruder "TEX30α" manufactured by Japan Steel Works, Ltd. equipped with one vent. The mixture was kneaded under the conditions of a screw rotation speed of 200 rpm, a discharge rate of 20 kg / hr, and a barrel temperature of 310°C. The molten resin extruded in strand form was rapidly cooled in a water bath and pelletized using a pelletizer to obtain polycarbonate resin composition pellets.

[0088] <Evaluation of Flame Retardancy: UL-94 (1.5 mm thick)> The resin composition pellets obtained above were dried at 120°C for 4 hours. Then, using a Sumitomo Heavy Industries SE50DUZ injection molding machine, a UL-94 test specimen with a length of 125 mm, a width of 13 mm, and a thickness of 1.5 mm was injection molded under the conditions of a cylinder temperature of 305°C, a mold temperature of 105°C, and a molding cycle of 40 seconds. The obtained UL test specimens were tested in accordance with the UL94 test defined by Underwriters Laboratories (UL) in the United States. The flammability results were classified as V-0, V-1, and V-2 from best to worst, and those that did not meet the specifications were classified as NG.

[0089] <Evaluation of Plating Performance (LDS Performance)> After drying the resin composition pellets obtained above at 120°C for 4 hours, a 90 mm × 60 mm × 2 mm thick flat test piece was injection molded using an injection molding machine (Sumitomo Heavy Industries, Ltd. "SE50DUZ") under the conditions of cylinder temperature 300°C and mold temperature 100°C. A 10 mm × 10 mm area of ​​the obtained flat test piece was irradiated using a Trumpf VMc1 laser irradiation device (wavelength 1064 nm, YAG laser, maximum output 15 W) at 80% output, frequency 10 kHz, and speed 1 m / s. The subsequent plating process was carried out in a 48°C plating bath of an electroless Enphone "ENPLATE LDS CU 400 PC". The plating performance (LDS performance) was evaluated by visually checking the thickness of the copper plated in 20 minutes according to the following criteria. A: All parts within the set range can be plated and have a very good appearance. B: Most parts within the set range can be plated, but the plating layer is thin. C: Not plated.

[0090] <Appearance Evaluation After Residence Molding> The pellets obtained by the method described above were dried at 80°C for 5 hours. Then, molded products (125 mm x 13 mm x 1.5 mm) were obtained using a Sumitomo Heavy Industries "SE50DUZ" mold, with a cylinder temperature of 300°C and a mold temperature of 100°C, adjusted to a residence time of 10 minutes. The appearance of the obtained molded products was observed and evaluated according to the following criteria: A: No appearance defects B: Slight appearance defects C: Many appearance defects

[0091] <Measurement of Fluorine Content (Unit: ppm by mass)> The fluorine content in the resin composition was quantified by combustion ion chromatography. Specifically, the polycarbonate resin composition pellets obtained above were heated in an argon atmosphere at 270°C for 10 minutes using an automated sample combustion device, the "AQF-100" manufactured by Mitsubishi Chemical Analytec Co., Ltd., and the amount of fluoride ions generated was quantified using the "ICS-90" manufactured by Nippon Dionex Co., Ltd. A calibration curve prepared from separately prepared standard substances was used to calculate the content. In Table 2-3, substances that were difficult to measure because they were below the detection limit of 5 ppm when analyzed by combustion ion chromatography are marked as "ND" (not detected). Resin compositions that do not contain PFAS compounds are naturally marked as ND. The fluorine content in the resin composition is preferably less than 500 ppm by mass, more preferably 400 ppm by mass or less, 300 ppm by mass or less, 100 ppm by mass or less, 50 ppm by mass or less, and particularly preferably 5 ppm by mass or less (ND).

[0092] <Transmittance (50 μm thickness, 700 nm)> The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours, and then a 50 μm thick film was formed using a Toyo Seiki Co., Ltd. press molding machine "Mini Test Press" at a temperature of 240°C and a press pressure of 25 MPa. The spectral transmittance (unit: %) in the thickness direction of this film was measured at a wavelength of 700 nm. The measurement was performed using a Shimadzu Corporation UV-2700 ultraviolet-visible light spectrophotometer with a C light source and a 2° field of view. The transmittance (unit: %) at 700 nm was measured and evaluated according to the following criteria: A: transmittance less than 5%, B: transmittance 5% or more and less than 20%, C: transmittance 20% or more and 50% or less, D: transmittance greater than 50%. When incorporated internally as an antenna component, a light shielding effect with a transmittance of less than 20% is preferable for concealing the antenna pattern, etc.

[0093] The evaluation results are shown in Table 2-3 below.

[0094]

[0095]

[0096] The polycarbonate resin composition of the present invention is an environmentally friendly material that clears various regulations such as PFAS, while possessing excellent flame retardancy, superior laser direct structuring performance, and excellent heat retention stability and light shielding properties. Therefore, it can be suitably used in various molded products.

Claims

1. A polycarbonate resin composition characterized by containing 10 to 80% by mass of an aromatic polycarbonate resin (A1) having a viscosity-average molecular weight of 50,000 to 90,000, with 0.5 to 50 parts by mass of a laser direct structuring additive (B), 0.01 to 1 part by mass of an organic sulfonic acid metal salt (C), and 0.1 to 2.5 parts by mass of a flame retardant aid (D) that does not contain phosphorus or halogen, per 100 parts by mass of polycarbonate resin (A) containing 10 to 80% by mass of an aromatic polycarbonate resin (A1) having a viscosity-average molecular weight of 50,000 to 90,000.

2. The polycarbonate resin composition according to claim 1, comprising 100 parts by mass of polycarbonate resin (A) containing 10 to 80% by mass of linear aromatic polycarbonate resin (A1) having a viscosity-average molecular weight of 50,000 to 90,000, 0.5 to 50 parts by mass of laser direct structuring additive (B), 0.01 to 1 part by mass of organic sulfonic acid metal salt (C), and 0.1 to 2.5 parts by mass of a flame retardant aid (D) that does not contain phosphorus or halogen.

3. The polycarbonate resin composition according to claim 1 or 2, wherein the fluorine content measured by combustion ion chromatography is less than 500 ppm by mass.

4. The polycarbonate resin composition according to claim 1 or 2, wherein the organic sulfonic acid metal salt (C) is an aromatic sulfonic acid metal salt.

5. The polycarbonate resin composition according to claim 1 or 2, wherein the flame retardant additive (D) that does not contain phosphorus or halogen is one or more of the following: a mineral containing aluminum or magnesium, or a silicone-based flame retardant additive.

6. The polycarbonate resin composition according to claim 1 or 2, wherein the UL-94 layer with a thickness of 1.5 mm is V-0.

7. The polycarbonate resin composition according to claim 1 or 2, wherein the spectral transmittance at a wavelength of 700 nm in the thickness direction, measured on a 50 μm thick film molded from the polycarbonate resin composition, is less than 20%.

8. The polycarbonate resin composition according to claim 1 or 2, for use in laser direct structuring molded articles.

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

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

11. A molded article comprising pellets of the polycarbonate resin composition described in claim 9.

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